Avermectins substituted in the 4″ and 4′-positions having pesticidal properties

ABSTRACT

What is described are a compound of the formula (I) Wherein A-B is —CH═CH— or —CH 2 —CH 2 —; n is 0 or 1; R 1 , is C 1 -C 12 alkyl, C 3 -C 8 cycloalkyl or C 2 -C 12 alkenyl; R 2  and R 3  for instance are either, (i) independently from each other for instance -Q, —C(═Y)-Q, or —C(═Y)—O-Q; or (ii) together form with the nitrogen atom to which they are bound a three- to seven-membered ring, (iii) together are ═C(R 4 )R 5 ; R 4  and R 5  are, independently from each other, for instance -Q, —C(═Y)-Q, or —C(═Y)—O-Q; Y is O or S; Q is for instance H or unsubstituted or mono- to pentasubstituted C 1 -C 12 alkyl; or, if appropriate, an E/Z isomer, E/Z isomer mixture and/or tautomer thereof; a process for preparing these compounds, their isomers and tautomers and the use of these compounds, their isomers and tautomers; pesticidal compositions whose active compound is selected from these compounds and their tautomers; intermediates for the preparation of the said compounds of the formula (I), methods for the preparation of the compounds of the formula (I), and a method for controlling pests using these compositions

This application is a 371 of International Application No.PCT/EP2004/000972 filed Feb. 3, 2004, which claims priority to GB0302548.3, filed Feb. 4, 2003, the contents of which are incorporatedherein by reference.

The invention provides (1) a compound of the formula (I)

wherein

A-B is —CH═CH— or —CH₂—CH₂—;

n is 0 or 1;

R₁ is C₁-C₁₂alkyl, C₃-C₈cycloalkyl or C₂-C₁₂alkenyl;

R₂ and R₃ are either,

(i) independently from each other, -Q, —C(═Y)-Q, —C(═Y)—O-Q,—C(═Y)—N(R₆)-Q, —SO₂Q, —SO₂N(R₆)Q or CN; or

(ii) together with the nitrogen atom to which they are bound form athree- to ten-membered ring, which may be monocyclic or bicyclic, whichmay be saturated or unsaturated, and that may contain, in addition tothe aforesaid nitrogen atom, one to two hetero atoms selected from thegroup consisting of N, O and S, and which is either unsubstituted orindependently of one another mono- to pentasubstituted with substituentsselected from OH, ═O, SH, ═S, halogen, CN, SCN, N₃, NO₂, aryl,C₁-C₁₂alkyl, C₃-C₈cycloalkyl, C₁-C₁₂alkoxy, C₃-C₈cycloalkoxy,C₁-C₁₂haloalkoxy, C₁-C₁₂alkylthio, C₁-C₁₂cycloalkylthio,C₁-C₁₂haloalkylthio, C₁-C₆alkoxy-C₁-C₆alkyl, C₂-C₈alkenyl,C₂-C₆alkenyloxy, C₂-C₆haloalkenyloxy, C₂-C₈alkynyl, C₃-C₆haloalkynyloxy,C₂-C₆alkenylthio, C₂-C₆haloalkenylthio, C₁-C₆alkylsulfinyl,C₃-C₈cycloalkylsulfinyl, C₁-C₆haloalkylsulfinyl,C₃-C₈halocycloalkylsulfinyl, C₂-C₆alkenylsulfinyl,C₂-C₆haloalkenylsulfinyl, C₁-C₆alkylsulfonyl, C₃-C₈cycloalkylsulfonyl,C₁-C₆haloalkylsulfonyl, C₃-C₈halocycloalkylsulfonylC₂-C₆alkenylsulfonyl, C₂-C₆haloalkenylsulfonyl, phenoxy,phenyl-C₁-C₆alkyl, trialkylsilyl; —C(═O)R₇, —O—C(═O)—R₈, —NH—C(═O)—R₈and —N(R₉)₂, wherein the two R₉ are independent of each other; or

(iii) together are ═C(R₄)R₅;

R₄ and R₅ are, independently from each other, -Q, —C(═Y)-Q, —C(═Y)—O-Q,—C(═Y)—N(R₆)-Q, —SO₂Q, —SO₂N(R₆)Q or CN; or

R₄ and R₅ are together with the carbon atom to which they are bound, athree- to ten-membered alkylene or a four- to seven-membered alkenylenebridge, wherein one CH₂ group in the alkylene or alkenylene may havebeen replaced by O, S or NR₉, and which is unsubstituted or mono totri-substituted;

Y is O or S;

R₆ is H, C₁-C₈alkyl, C₃-C₈cycloalkyl, C₂-C₈alkenyl, C₂-C₈alkynyl,phenyl, benzyl or —C(═O)R₇;

Q is H, unsubstituted or mono- to pentasubstituted C₁-C₁₂alkyl,unsubstituted or mono- to pentasubstituted C₂-C₁₂alkenyl, unsubstitutedor mono- to pentasubstituted C₂-C₁₂alkynyl, unsubstituted or mono- topentasubstituted C₃-C₁₂-cycloalkyl, unsubstituted or mono- topentasubstituted C₅-C₁₂-cycloalkenyl, unsubstituted or mono- topentasubstituted aryl, or unsubstituted or mono- to pentasubstitutedheterocyclyl;

and wherein the substituents of the alkyl, alkenyl, alkynyl, alkylene,alkenylene, cycloalkyl, cycloalkenyl, aryl and heterocyclyl radicalsmentioned under Q, R₂, R₃, R₄, R₅ and R₆ are selected from the groupconsisting of OH, ═O, SH, ═S, halogen, CN, SCN, SF₅, N₃, NO₂, aryl,C₃-C₈cycloalkyl, C₁-C₁₂haloalkyl, C₃-C₈halocycloalkyl, C₁-C₁₂alkoxy,C₃-C₈cycloalkoxy, C₁-C₁₂haloalkoxy, C₁-C₁₂alkylthio,C₁-C₁₂cycloalkylthio, C₁-C₁₂haloalkylthio, C₁-C₆alkoxy-C₁-C₆alkyl,C₁-C₆-alkoxy-C₁-C₆-alkoxy, C₂-C₈alkenyl, C₂-C₆alkenyloxy,C₂-C₆haloalkenyl, C₂-C₆haloalkenyloxy, C₂-C₈alkynyl, C₂-C₆haloalkynyl,C₃-C₆alkynyloxy, C₃-C₆haloalkynyloxy, C₂-C₆alkenylthio,C₂-C₆haloalkenylthio, C₁-C₆alkylsulfinyl, C₃-C₈cycloalkylsulfinyl,C₁-C₆haloalkylsulfinyl, C₃-C₈halocycloalkylsulfinyl,C₂-C₆alkenylsulfinyl, C₂-C₆haloalkenylsulfinyl, C₁-C₆alkylsulfonyl,C₃-C₈cycloalkylsulfonyl, C₁-C₆haloalkylsulfonyl,C₃-C₈halocycloalkylsulfonyl C₂-C₆alkenylsulfonyl,C₂-C₆haloalkenylsulfonyl, phenoxy, phenyl-C₁-C₆alkyl, trialkylsilyl;—C(═O)R₇, —O—C(═O)—R₈, —NH—C(═O)—R₈, —N(R₉)₂, wherein the two R₉ areindependent of each other, aryl, benzyl, heterocyclyl, aryloxy,benzyloxy, heterocyclyloxy, arylthio, benzylthio and heterocyclylthio;wherein the aryl, heterocyclyl, aryloxy, benzyloxy, heterocyclyloxy,arylthio, benzylthio and heterocyclylthio radicals are unsubstituted or,depending on the possibilities of substitution on the ring, are mono- topentasubstituted by substituents selected from the group consisting ofOH, ═O, SH, ═S, halogen, CN, NO₂, C₁-C₁₂alkyl, C₁-C₁₂hydroxyalkyl,C₃-C₈cycloalkyl, C₁-C₁₂haloalkyl, C₁-C₁₂alkoxy, C₁-C₁₂haloalkoxy,C₁-C₁₂alkylthio, C₁-C₁₂haloalkylthio, C₁-C₆alkoxy-C₁-C₆alkyl,dimethylamino-C₁-C₆alkoxy, C₂-C₈alkenyl, C₂-C₈alkynyl, phenoxy,phenyl-C₁-C₆alkyl; methylenedioxy, —C(═O)R₇, —O—C(═O)—R₈, —NH—C(═O)R₇,—N(R₉)₂, wherein the two R₉ are independent of each other;C₁-C₆alkylsulfinyl, C₃-C₈cycloalkylsulfinyl, C₁-C₆haloalkylsulfinyl,C₃-C₈halocycloalkylsulfinyl, C₁-C₆alkylsulfonyl,C₃-C₈cycloalkylsulfonyl, C₁-C₆haloalkylsulfonyl andC₃-C₈halocycloalkylsulfonyl;

R₇ is H, OH, SH, —N(R₉)₂ wherein the two R₉ are independent of eachother, C₁-C₂₄alkyl, C₂-C₁₂alkenyl, C₁-C₈hydroxyalkyl, C₁-C₁₂haloalkyl,C₁-C₁₂alkoxy, C₁-C₁₂haloalkoxy, C₁-C₆alkoxy-C₁-C₆alkyl,C₁-C₆alkoxy-C₁-C₆alkoxy, C₁-C₆alkoxy-C₁-C₆alkoxy-C₁-C₆alkyl,C₁-C₁₂alkylthio, C₂-C₈alkenyloxy, C₃-C₈alkynyloxy; aryl, benzyl,heterocyclyl, aryloxy, benzyloxy, heterocyclyloxy; or aryl, benzyl,heterocyclyl, aryloxy, benzyloxy or heterocyclyloxy, which are mono- totrisubstituted in the ring independently of one another by halogen,nitro, C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆haloalkyl or C₁-C₆haloalkoxy;

R₈ is H, C₁-C₆alkyl that is optionally substituted with one to fivesubstituents selected from the group consisting of halogen, C₁-C₆alkoxy,hydroxy and cyano, C₁-C₈-cycloalkyl, aryl, benzyl, heteroaryl; or aryl,benzyl or heteroaryl, which, depending on the possibilities ofsubstitution on the ring, are mono- to trisubstituted by substituentsselected from the group consisting of OH, halogen, CN, NO₂, C₁-C₁₂alkyl,C₁-C₁₂haloalkyl, C₁-C₁₂alkoxy, C₁-C₁₂haloalkoxy, C₁-C₁₂alkylthio andC₁-C₁₂haloalkylthio; and

R₉ is H; C₁-C₆alkyl, which is optionally substituted with one to fivesubstituents selected from the group consisting of halogen, C₁-C₆alkoxy,hydroxy and cyano; C₁-C₈-cycloalkyl, aryl, benzyl, heteroaryl; or aryl,benzyl or heteroaryl, which, depending on the possibilities ofsubstitution on the ring, are mono- to trisubstituted by substituentsselected from the group consisting of OH, halogen, CN, NO₂, C₁-C₁₂alkyl,C₁-C₁₂haloalkyl, C₁-C₁₂alkoxy, C₁-C₁₂haloalkoxy, C₁-C₁₂alkylthio andC₁-C₁₂haloalkylthio;

or, if appropriate, an E/Z isomer, E/Z isomer mixture and/or tautomerthereof, in each case in fro form or in salt form;

a process for preparing these compounds, their isomers and tautomers andthe use of these compounds, their isomers and tautomers; pesticideswhose active compound is selected from these compounds and theirtautomers; and a method for controlling pests using these compositions.

Hereinbefore and hereinafter, the bond at the ε-position marked by thesymbol—in formulae (I) to (III) indicates that the (S)— as well as the(R)-isomer is meant.

The literature proposes certain macrolide compounds for controllingpests. However, the biological properties of these known compounds arenot entirely satisfactory, and, as a consequence, there is still a needfor providing further compounds having pesticidal properties, inparticular for the control of insects and representatives of the orderAcarina. According to the invention, this object is achieved byproviding the present compounds of the formula (I).

The compounds claimed according to the invention are derivatives ofAvermectin. Avermectins are known to the person skilled in the art. Theyare a group of structurally closely related pesticidally activecompounds which are obtained by fermenting a strain of the microorganismStreptomyces avermitilis. Derivatives of Avermectins can be obtained byconventional chemical syntheses.

The Avermectins which can be obtained from Streptomyces avermitilis arereferred to as A1a, A1b, A2a, A2b, B1a, B1b, B2a and B2b. The compoundsreferred to as “A” and “B” have a methoxy radical and an OH group,respectively, in the 5-position. The “a” series and the “b” series arecompounds in which the substituent R₁ (in position 25) is a sec-butylradical and an isopropyl radical, respectively. The number 1 in the nameof the compounds means that carbon atoms 22 and 23 are linked by doublebonds; the number 2 means that they are linked by a single bond and thatthe C atom 23 carries an OH group. The above nomenclature is adhered toin the description of the present invention to denote the specificstructure type in the not naturally occurring Avermectin derivativesaccording to the invention which corresponds to the naturally occurringAvermectin. What is for instance claimed according to the invention arederivatives of compounds of the B1 series, in particular mixtures ofderivatives of Avermectin B1, especially B1a and B1b, along withderivatives having a single bond between carbon atoms 22 and 23, andderivatives having other substituents in the 25-position, as well as thecorresponding monosaccharides.

Some of the compounds of the formula (I) can be present as tautomers.Accordingly, hereinabove and hereinbelow, the compounds of the formula(I) are, if appropriate, also to be understood as including thecorresponding tautomers, even if the latter are not specificallymentioned in each case.

The compounds of formula (I) and, where applicable, their tautomers canform salts, for example acid addition salts. These acid addition saltsare formed, for example, with strong inorganic acids, such as mineralacids, for example sulfuric acid, a phosphoric acid or a hydrohalicacid, with strong organic carboxylic acids, such as unsubstituted orsubstituted, for example halo-substituted, C₁-C₄alkanecarboxylic acids,for example acetic acid, unsaturated or saturated dicarboxylic acids,for example oxalic acid, malonic acid, maleic acid, fumaric acid orphthalic acid, hydroxycarboxylic acids, for example ascorbic acid,lactic acid, malic acid, tartaric acid or citric acid, or benzoic acid,or with organic sulfonic acids, such as unsubstituted or substituted,for example halo-substituted, C₁-C₄alkane- or aryl-sulfonic acids, forexample methane- or p-toluene-sulfonic acid. Compounds of formula (I)that have at least one acidic group can furthermore form salts withbases. Suitable salts with bases are, for example, metal salts, such asalkali metal salts or alkaline earth metal salts, for example sodium,potassium or magnesium salts, or salts with ammonia or with an organicamine, such as morpholine, piperidine, pyrrolidine, a mono-, di- ortri-lower alkylamine, for example ethylamine, diethylamine,triethylamine or dimethylpropylamine, or a mono-, di- ortrihydroxy-lower alkylamine, for example mono-, di- or tri-ethanolamine.Corresponding internal salts may also be formed where appropriate. Thefree form is preferred. Among the salts of the compounds of formula (I),the agrochemically advantageous salts are preferred. Hereinbefore andhereinafter, any reference to the free compounds of formula (I) or theirsalts is to be understood as including, where appropriate, also thecorresponding salts or the free compounds of formula (I), respectively.The same applies to tautomers of compounds of formula (I) and saltsthereof.

Unless defined otherwise, the general terms used hereinabove andhereinbelow have the meanings given below.

Unless defined otherwise, carbon-containing groups and compounds eachcontain from 1 up to and including 6, preferably from 1 up to andincluding 4, especially 1 or 2, carbon atoms.

Halogen—as a group per se and also as a structural element of othergroups and compounds, such as haloalkyl, haloalkoxy and haloalkylthio—isfluorine, chlorine, bromine or iodine, in particular fluorine, chlorineor bromine, especially fluorine or chlorine.

Alkyl—as a group per se and also as a structural element of other groupsand compounds, such as haloalkyl, alkoxy and alkylthio—is, in each casetaking into account the number of carbon atoms contained in each case inthe group or compound in question, either straight-chain, i.e. methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, or branched, forexample isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentylor isohexyl.

Cycloalkyl—as a group per se and also as a structural element of othergroups and compounds, such as, for example, of halocycloalkyl,cycloalkoxy and cycloalkylthio—is, in each case taking into account thenumber of carbon atoms contained in each case in the group or compoundin question, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl or cyclooctyl.

Alkenyl—as a group per se and also as a structural element of othergroups and compounds—is, taking into account the number of carbon atomsand conjugated or isolated double bonds contained in the group, eitherstraight-chain, for example vinyl, allyl, 2-butenyl, 3-pentenyl,1-hexenyl, 1-heptenyl, 1,3-hexadienyl or 1,3-octadienyl, or branched,for example isopropenyl, isobutenyl, isoprenyl, tert-pentenyl,isohexenyl, isoheptenyl or isooctenyl. Preference is given to alkenylgroups having 3 to 12, in particular 3 to 6, especially 3 or 4, carbonatoms.

Alkynyl—as a group per se and also as a structural element of othergroups and compounds—is, in each case taking into account the number ofcarbon atoms and conjugated or isolated double bonds contained in thegroup or compound in question, either straight-chain, for exampleethynyl, propargyl, 2-butynyl, 3-pentynyl, 1-hexynyl, 1-heptynyl,3-hexen-1-ynyl or 1,5-heptadien-3-ynyl, or branched, for example3-methylbut-1-ynyl, 4-ethylpent-1-ynyl, 4-methylhex-2-ynyl or2-methylhept-3-ynyl. Preference is given to groups —CH₂—C₂-C₁₁alkynyl,in particular —CH₂—C₂-C₅alkynyl, especially —CH₂—C₂-C₃alkynyl.

Alkylene and alkenylene are straight-chain or branched bridge members;they are in particular —CH₂—CH₂—CH₂—, —CH₂—CH₂—CH₂—CH₂—,—CH₂—CH₂—CH₂—CH₂—CH₂—, —CH₂(CH₃)CH₂—CH₂—, —CH₂C(CH₃)₂—CH₂—, —CH₂—CH═CH—,—CH₂—CH═CH—CH₂— or —CH₂—CH═CH—CH₂—CH₂—.

Halogen-substituted carbon-containing groups and compounds, such as, forexample, halogen-substituted alkyl, alkenyl, alkynyl, cycloalkyl, alkoxyor alkylthio, can be partially halogenated or perhalogenated, where inthe case of polyhalogenation the halogen substituents can be identicalor different. Examples of haloalkyl—as a group per se and also as astructural element of other groups and compounds, such as haloalkoxy orhaloalkylthio—are methyl which is mono- to trisubstituted by fluorine,chlorine and/or bromine, such as CHF₂ or CF₃; ethyl which is mono- topentasubstituted by fluorine, chlorine and/or bromine, such as CH₂CF₃,CF₂CF₃, CF₂CCl₃, CF₂CHCl₂, CF₂CHF₂, CF₂CFCl₂, CF₂CHBr₂, CF₂CHClF,CF₂CHBrF or CClFCHClF; propyl or isopropyl which is mono- toheptasubstituted by fluorine, chlorine and/or bromine, such asCH₂CHBrCH₂Br, CF₂CHFCF₃, CH₂CF₂CF₃, CF(CF₃)₂ or CH(CF₃)₂; butyl or oneof its isomers, mono- to nonasubstituted by fluorine, chlorine and/orbromine, such as CF(CF₃)CHFCF₃ or CH₂(CF₂)₂CF₃; pentyl or one of itsisomers, mono- to undecasubstituted by fluorine, chlorine and/orbromine, such as CF(CF₃)(CHF₂)CF₃ or CH₂(CF₂)₃CF₃; and hexyl or one ofits isomers, mono- to tridecasubstituted by fluorine, chlorine and/orbromine, such as (CH₂)₄CHBrCH₂Br, CF₂(CHF)₄CF₃, CH₂(CF₂)₄CF₃ orC(CF₃)₂(CHF)₂CF₃.

Aryl is in particular phenyl, naphthyl, anthracenyl, phenanthrenyl,perylenyl or fluorenyl, preferably phenyl.

Heterocyclyl is understood as being a three- to seven-memberedmonocyclic ring, which may be saturated or unsaturated, and thatcontains from one to three hetero atoms selected from the groupconsisting of N, O and S, especially N and S; or a bicyclic ring-systemhaving from 8 to 14 ring atoms, which may be saturated or unsaturated,and that may contain either in only one ring or in both ringsindependently of one another, one or two hetero atoms selected from N, Oand S.

Heterocyclyl is in particular piperidinyl, piperazinyl, oxiranyl,morpholinyl, thiomorpholinyl, pyridyl, N-oxidopyridinio, pyrimidyl,pyrazinyl, s-triazinyl, 1,2,4-triazinyl, thienyl, furanyl,dihydrofuranyl, tetrahydrofuranyl, pyranyl, tetrahydropyranyl, pyrrolyl,pyrrolinyl, pyrrolidinyl, pyrazolyl, imidazolyl, imidazolinyl,thiazolyl, isothiazolyl, triazolyl, oxazolyl, thiadiazolyl, thiazolinyl,thiazolidinyl, oxadiazolyl, maleimidoyl, succinimidoyl, phthalimidoyl,benzothienyl, quinolinyl, quinoxalinyl, benzofuranyl, benzimidazolyl,benzpyrrolyl, benzthiazolyl, indolinyl, isoindolinyl, cumarinyl,indazolyl, benzothiophenyl, benzofuranyl, pteridinyl or purinyl, whichare preferably attached via a C atom; thienyl, benzofuranyl,benzothiazolyl, tetrahydropyranyl or indolyl is preferred; in particularpyridyl or thiazolyl. The said heterocyclyl radicals may preferrably beunsubstituted or—depending on the substitution possibilities on the ringsystem—substituted by 1 to 4 substituents selected from the groupconsisting of halogen, ═O, —OH, ═S, SH, nitro, C₁-C₆alkyl,C₁-C₆hydroxyalkyl, C₁-C₆alkoxy, C₁-C₆haloalkyl, C₁-C₆haloalkoxy, phenyl,benzyl, —C(═O)—R₈ and —CH₂—C(═O)—R₈.

In the context of the present invention, preference is given to

(2) compounds according to group (1) of the formula (I) in which R₁ isisopropyl or sec-butyl, preferably to those in which a mixture of theisopropyl and the sec-butyl derivative is present;

(3) compounds according to group (1) of the formula (I) in which R₁ iscyclohexyl;

(4) compounds according to group (1) of the formula (I) in which R₁ is1-methyl-butyl;

(5) compounds according to one of groups (1) to (4) of the formula (I)in which the configuration at the ε-position is (S);

(6) compounds according to one of groups (1) to (4) of the formula (I)in which the configuration at the ε-position is (R);

(7) compounds according to one of groups (1) to (6) of the formula (I)in which n is 1;

(8) compounds according to one of groups (1) to (6) of the formula (I)in which n is 0;

(9) compounds according to one of groups (1) to (8) of the formula (I)in which A-B is —CH═CH—;

(10) compounds according to one of groups (1) to (8) of the formula (I)in which A-B is —CH₂—CH₂—;

(11) compounds according to one of groups (1) to (10) of the formula (I)in which R₂ is -Q;

(12) compounds according to one of groups (1) to (10) of the formula (I)in which R₂ is —C(═O)-Q, —C(═O)—O-Q, —C(═O)—N(R₆)-Q, —SO₂Q or—SO₂N(R₆)Q;

(13) compounds according to one of groups (1) to (12) of the formula (I)in which R₃H, unsubstituted or mono- to pentasubstituted C₁-C₁₂alkyl,unsubstituted or mono- to pentasubstituted C₂-C₁₂alkenyl;

(14) compounds according to one of groups (1) to (10) of the formula (I)in which R₂ and R₃together form with the nitrogen atom to which they arebound a five- to seven-membered ring, which may be monocyclic orbicyclic, which may be saturated or unsaturated, and that may contain,in addition to the aforesaid nitrogen atom, one or two hetero atomsselected from the group consisting of N, O and S, and which is eitherunsubstituted or independently of one another mono-trisubstituted withsubstituents selected from OH, ═O, SH, ═S, halogen, CN, NO₂, aryl,C₁-C₁₂alkyl, C₃-C₈cycloalkyl, C₁-C₁₂haloalkyl, C₁-C₁₂alkoxy,C₁-C₁₂haloalkoxy, C₁-C₁₂alkylthio, C₁-C₁₂haloalkylthio;

(15) compounds according to one of groups (1) to (10) or (14) of theformula (I) in which R₂ and R₃ together are a four- to six memberedalkylene bridge, which is unsubstituted or mono to tri-substituted;especially unsubstituted;

(16) compounds according to one of groups (1) to (10), (14) or (15) ofthe formula (I) in which and NR₂R₃ is phtalimidoyl, maleimidoyl,succinimidoyl, which are unsubstituted or mono- to tetrasubstituted inthe ring independently of one another by OH, halogen, CN, NO₂, aryl,C₁-C₁₂alkyl, C₃-C₈cycloalkyl, C₁-C₁₂haloalkyl, C₁-C₁₂alkoxy,C₁-C₁₂haloalkoxy, C₁-C₁₂alkylthio, C₁-C₁₂haloalkylthio,C₁-C₆alkoxy-C₁-C₆alkyl, C₂-C₈alkenyl, C₂-C₈alkynyl, phenoxy,phenyl-C₁-C₆alkyl; —C(═O)R₇, —O—C(═O)—R₈, —NH—C(═O)R₈, —N(R₉)₂, whereinthe two R₉ are independent of each other; C₁-C₆alkylsulfinyl,C₃-C₈cycloalkylsulfinyl, C₁-C₆haloalkylsulfinyl,C₃-C₈halocycloalkylsulfinyl, C₁-C₆alkylsulfonyl,C₃-C₈cycloalkylsulfonyl, C₁-C₆haloalkylsulfonyl andC₃-C₈halocycloalkylsulfonyl;

(17) compounds according to one of groups (1) to (13) of the formula (I)in which Q is unsubstituted or mono-substituted aryl or unsubstituted ormono-substituted heterocyclyl;

(18) compounds according to one of groups (1) to (13) of the formula (I)in which Q is H, C₁-C₁₂alkyl, C₂-C₁₂alkenyl, C₃-C₁₂alkynyl orC₃-C₁₂-cycloalkyl, which are all unsubstituted; preferably H orC₁-C₁₂alkyl;

(19) compounds according to one of groups (1) to (13) of the formula (I)in which Q is C₃-C₁₂-cycloalkyl, C₅-C₁₂-cycloalkenyl, aryl orheterocyclyl, which are all unsubstituted.

Special preference is given within the scope of the invention to thecompounds of formula (I) listed in the Tables and, where applicable,their tautomers, their mixtures of tautomers, their E/Z isomers,mixtures of E/Z isomers and diastereomers.

The invention also provides a process for preparing the compounds of theformula (I) and, if appropriate, tautomers thereof, wherein R₂ and R₃are defined as under (1) which comprises

(A) reacting a compound of formula

wherein n and A-B are as defined in formula (I), G is a protecting groupand Z is a leaving group such as chloride, bromide, iodide,alkylsulfonate, haloalkylsulfonate or arylsulfonate, and which is knownor can be prepared by methods known per se, with a compound of formulaR₂R₃NOH in which R₂ and R₃ have the meanings as given above for formula(I) under (1), to form a compound of the formula

wherein R₂, R₃, n, A-B are as defined for formula (I) and G is aprotecting group; and

(B) removing the protecting group G of the compound of formula (III) soobtained, or

(C) for preparing a compound of the formula (I) wherein R₁, n and A-Bare as defined for formula (I) and R₂ and R₃ are H, reacting a compoundof formula (I), wherein R₁, n and A-B are as defined for formula (I)under (1), and R₂ and R₃ are as defined for formula (I) under (ii), witha compound of formula (Q)₂N—NH₂, or with a compound of formula Q-NH₂, inwhich the substituents Q independently of each other have the samemeaning as given above under (1) for formula (I), or with a reducingagent; or

(D) for forming a compound of the formula (I), wherein R₁, n and A-B areas defined for formula (I) and R₂ and R₃ have the meaning as definedunder (iii) for formula (I), reacting a compound of formula (I), inwhich n, A-B and R₁ have the same meanings as given above under (1) forformula (I) and R₂ and R₃ are H, with a compound R₄—CO—R₅, in which R₄and R₅ have the same meanings as given above under (iii) for formula(I);

(E) for forming a compound of the formula (I), wherein R₁, n and A-B areas defined for formula (I) and R₂ and R₃ have the meanings as definedunder (i) for formula (I), reacting a compound of formula (I), in whichn, A-B, and R₁ have the same meanings as given above under (1) forformula (I), and R₂ and R₃ are H, with a compound Q-X₂, with a compoundQ-C(═O)—Cl, Q-O—C(═O)—Cl, Q-C(═S)—Cl, Q-O—C(═S)—Cl, Q-SO₂—Cl,Q-N(R₆)—SO₂—Cl, Q-N(R₆)—C(═O)—Cl, Q-N(R₆)—C(═S)—Cl, Q-N═C═O or with acompound Q-N═C═S, in which Q and R₆ have the same meaning as given aboveunder (1) for formula (I) and X₂ is chloride, bromide, iodide,alkylsulfonate, haloalkylsulfonate or arylsulfonate, or

(F) reacting a compound of formula (III), in which n, A-B, R₁ and G havethe same meanings as given above under (A) for formula (III) and inwhich R₂ and R₃ are H with a compound of the formula Q-X₂, Q-C(═O)—Cl,Q-O—C(═O)—Cl, Q-C(═S)—Cl, Q-O—C(═S)—Cl, Q-SO₂—Cl, Q-N(R₆)—SO₂—Cl,Q-N(R₆)—C(═O)—Cl, Q-N(R₆)—C(═S)—Cl, Q-N═C═O or Q-N═C═S, in which Q andR₆ have—with the exception of H—the same meaning as given above under(1) for formula (I) and X₂ is chloride, bromide, iodide, alkylsulfonate,haloalkylsulfonate or arylsulfonate, to form a compound of formula(III), in which n, A-B, R₁ and G have the same meanings as given abovefor formula (III), and in which R₂ and R₃ have the same meanings asgiven above under (i) for formula (I), provided that at least one of thesubstituents is not H; and

(G) removing the protecting group G of the compound of formula (III) soobtained, as described under (B), to form a compound of formula (I).

The reactions described hereinabove and hereinbelow are carried out in amanner known per se, for example in the absence or, customarily, in thepresence of a suitable solvent or diluent or of a mixture thereof, thereactions being carried out, as required, with cooling, at roomtemperature or with heating, for example in a temperature range ofapproximately from −80° C. to the boiling temperature of the reactionmedium, preferably from approximately 0° C. to approximately +150° C.,and, if necessary, in a closed vessel, under pressure, under an inertgas atmosphere and/or under anhydrous conditions. Especiallyadvantageous reaction conditions can be found in the Examples.

The reaction time is not critical; a reaction time of from about 0.1 toabout 24 hours, especially from about 0.5 to about 10 hours, ispreferred.

The product is isolated by customary methods, for example by means offiltration, crystallisation, distillation or chromatography, or anysuitable combination of such methods.

The starting materials mentioned hereinabove and hereinbelow that areused for the preparation of the compounds of formula (I) and, whereapplicable, their tautomers are known or can be prepared by methodsknown per se, e.g. as indicated below.

Process Variant (A):

Examples of solvents and diluents include: aromatic, aliphatic andalicyclic hydrocarbons and halogenated hydrocarbons, such as benzene,toluene, xylene, mesitylene, tetraline, chlorobenzene, dichlorobenzene,bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane,trichloromethane, tetrachloromethane, dichloroethane, trichloroethene ortetrachloroethene; ethers, such as diethyl ether, dipropyl ether,diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethyleneglycol monomethyl ether, ethylene glycol monoethyl ether, ethyleneglycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran ordioxane; alcohols, such as methanol, ethanol, propanol, isopropanol,butanol, ethylene glycol or glycerol; carboxylic acids, such as aceticacid, pivalic acid or formic acid; ketones, such as acetone, methylethyl ketone or methyl isobutyl ketone; carboxylic acid esters, such asmethyl acetate, ethyl acetate, or esters of benzoic acid; amides, suchas N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide,N-methylpyrrolidone or hexamethylphosphoric acid triamide; nitriles,such as acetonitrile or propionitrile; and sulfoxides, such as dimethylsulfoxide; and also water; or mixtures of the mentioned solvents;Preference is given to ethers, nitriles and amides, or mixtures thereof;acetonitrile is especially preferred.

Protecting groups G in the compounds of formulae (II) and (III) include:alkyl ether radicals, such as methoxymethyl, methylthiomethyl,tert-butylthiomethyl, benzyloxymethyl, p-methoxybenzyl,2-methoxyethoxymethyl, 2,2,2-trichloroethoxymethyl,2-(trimethylsilyl)ethoxymethyl, tetrahydropyranyl, tetrahydrofuranyl,1-ethoxyethyl, 1-(2-chloroethoxy)ethyl, 1-methyl-1-methoxyethyl,1-methyl-1-benzyloxyethyl, trichloroethyl, 2-trimethylsilylethyl,tert-butyl, allyl, p-methoxyphenyl, 2,4-dinitrophenyl, benzyl,p-methoxybenzyl, o-nitrobenzyl, p-nitrobenzyl, triphenylmethyl;trialkylsilyl radicals, such as trimethylsilyl, triethylsilyl,dimethyl-tert-butylsilyl, dimethyl-isopropylsilyl,dimethyl-1,1,2-trimethylpropylsilyl, diethyl-isopropylsilyl,dimethyl-tert-hexylsilyl, but also phenyl-tert-alkylsilyl groups, suchas diphenyl-tert-butylsilyl; esters, such as formates, acetates,chloroacetates, dichloroacetates, trichloroacetates, trifluoroacetates,methoxyacetates, phenoxyacetates, pivaloates, benzoates; alkylcarbonates, such as methyl-, 9-fluorenylmethyl-, ethyl-,2,2,2-trichloroethyl-, 2-(trimethylsilyl)ethyl-, vinyl-, allyl-,benzyl-, p-methoxybenzyl-, o-nitrobenzyl-, p-nitrobenzyl-, but alsop-nitrophenyl-carbonate.

Preference is given to trialkylsilyl radicals, such as trimethylsilyl,triethylsilyl, dimethyl-tert-butylsilyl, diphenyl-tert-butylsilyl,esters, such as methoxyacetates and phenoxyacetates, and carbonates,such as 9-fluorenylmethylcarbonates and allylcarbonates.Dimethyl-tert-butylsilyl ether is especially preferred.

The reactions are advantageously carried out in a temperature range offrom about −70° C. to the boiling point of the solvent used; preferencebeing given to reaction at −10° C. to 25° C.; in the presence of a base,for example an inorganic base, such as sodium hydroxide, potassiumhydroxide, sodium carbonate or sodium bicarbonate, or an organic base,such as pyridine, triethylamine, N-ethyl-N,N-diisopropylamine,1,8-diazabicyclo[5.4.0]undec-7-ene, or 1,5-diazabicyclo[4.3.0]non-5-ene;or without the presence of a base; preference being given to1,8-diazabicyclo[5.4.0]undec-7-ene.

Examples of a compound R₂R₃N—OH include substituted or unsubstitutedN-hydroxymaleimides and N-hydroxyphtalimides, for exampleN-hydroxyphtalimide.

In a preferred embodiment of Variant (A) the reaction is carried outwith N-hydroxyphtalimide at 0° C., in acetonitrile in the presence of1,8-diazabicyclo[5.4.0]undec-7-ene.

Especially preferred conditions for this process variant are describedin Examples A2.1 and A4.1.

Process Variant (B):

Examples of solvents and diluents are the same as those mentioned underProcess variant A. Preference is given to ethers; tetrahydrofuran isespecially preferred.

The reactions are advantageously carried out in a temperature range ofapproximately from −70° C. to 100° C., preferably at from −10° C. to 25°C.

There are suitable for the removal of the protecting group Lewis acids,such as hydrochloric acid, methanesulfonic acid, BF₃*OEt₂, HF inpyridine, Zn(BF₄)₂*H₂O, p-toluenesulfonic acid, AlCl₃, HgCl₂; ammoniumfluoride, such as tetrabutylammonium fluoride; bases, such as ammonia,trialkylamine or heterocyclic bases; hydrogenolysis with a catalyst,such as palladium-on-carbon; reducing agents, such as sodium borohydrideor tributyltin hydride with a catalyst, such as Pd(PPh₃)₄, or also zincwith acetic acid.

Preference is given to acids, such as methanesulfonic acid or HF inpyridine; sodium borohydride with Pd(0); bases, such as ammonia,triethylamine or pyridine; especially acids, such as HF in pyridine ormethanesulfonic acid.

In a preferred embodiment of variant (B) the reaction is carried outwith HF in pyridine at room temperature, in tetrahydrofuran.

Especially preferred conditions for the reaction are described inExample A2.1 and A4.1.

Process Variant (C):

Examples of solvents and diluents are the same as those mentioned underProcess variant A. Preference is given to alcohols; ethanol isespecially preferred.

The reactions are advantageously carried out in a temperature range offrom about −70° C. to the boiling point of the solvent used; preferencebeing given to reaction at 0° C. to 30° C.;

Examples of compounds of the formula (Q)₂N—NH₂ include hydrazines, forexample hydrazine or methylhydrazine.

Examples of reducing agents are known to a person skilled in the art,they include hydrides; especially suitable are borohydrides, for examplesodium borohydride or sodium cyanoborohydride.

In a preferred embodiment of variant (C) the reaction is carried outwith hydrazine monohydrate at room temperature, in ethanol.

Especially preferred conditions for the reaction are described inExample A2.2 and A4.2.

Process Variant (D):

Examples of solvents and diluents are the same as those mentioned underProcess variant A. Preference is given to aromatic hydrocarbons, ormixtures thereof; toluene, dioxan and water are especially preferred.

The reactions are advantageously carried out in a temperature range offrom about −70° C. to the boiling point of the solvent used; preferencebeing given to reaction at 25° C. to 80° C.; in the presence of acatalyst such as pyridinium p-toluenesulfonate; or without a catalyst.

Examples of compound R₄—CO—R₅ include ketones and aldehydes, for exampleacetaldehyde, glycolaldehyde, glyoxylic acid, benzaldehyde, acetone orcyclopentanone.

In a preferred embodiment of variant (D) the reaction is carried out intoluene at room temperature in the presence of pyridinium p-toluenesulfonate.

In another preferred embodiment of variant (D) the reaction is carriedout in dioxan and water at room temperature in the presence ofpyridinium p-toluene sulfonate.

In another preferred embodiment of variant (D) the reaction is carriedout in toluene at room temperature.

Especially preferred conditions for the reaction are described inExample A1.1, A1.2, A1.13 and A1.16.

Process Variant (E):

Examples of solvents and diluents are the same as those mentioned underProcess variant A. Preference is given to esters and water, or mixturesthereof; ethyl acetate and water are especially preferred.

The reactions are advantageously carried out in a temperature range offrom about −70° C. to the boiling point of the solvent used; preferencebeing given to reaction at 25° C. to 80° C.; in the presence of a base,for example an inorganic base, such as sodium hydroxide, potassiumhydroxide, sodium carbonate or sodium bicarbonate, or an organic base,such as pyridine, triethylamine, N-ethyl-N,N-diisopropylamine,1,8-diazabicyclo[5.4.0]undec-7-ene, or 1,5-diazabicyclo[4.3.0]non-5-ene;or without the presence of a base; preference being given to sodiumbicarbonate.

In a preferred embodiment of Variant (E) the reaction is carried out inthe presence of bicarbonate at room temperature, in a mixture of ethylacetate and water as the solvent.

Especially preferred conditions for the reaction are described inExample A2.11.

Process Variant (F):

Examples of solvents and diluents are the same as those mentioned underProcess variant A. Preference is given to halogenated hydrocarbons, ormixtures thereof; dichloromethane is especially preferred.

The reactions are advantageously carried out in a temperature range offrom about −70° C. to the boiling point of the solvent used; preferencebeing given to reaction at 25° C. to 80° C.; in the presence of a base,for example an inorganic base, such as sodium hydroxide, potassiumhydroxide, sodium carbonate or sodium bicarbonate, or an organic base,such as pyridine, triethylamine, N-ethyl-N,N-diisopropylamine,1,8-diazabicyclo[5.4.0]undec-7-ene, or 1,5-diazabicyclo[4.3.0]non-5-ene;or without the presence of a base; preference being given to pyridine.

In a preferred embodiment of Variant (E) the reaction is carried out inthe presence of bicarbonate at room temperature, in a mixture of ethylacetate and water as the solvent.

Especially preferred conditions for the reaction are described inExample A2.11.

Process Variant (G) is Carried Out by Analogy to Process Variant (B).

The comments made above in connection with tautomers of compounds of theformula (I) apply analogously to the staring materials and intermediatesmentioned hereinbefore and hereinbelow with respect to their tautomers.

The compounds of formula (I) may be in the form of one of the possibleisomers or in the form of a mixture thereof, in the form of pure isomersor in the form of an isomeric mixture, i.e. in the form of adiastereomeric mixture; the invention relates both to the pure isomersand to the diastereomeric mixtures and is to be interpreted accordinglyhereinabove and hereinbelow, even if stereochemical details are notmentioned specifically in every case.

The diastereomeric mixtures can be resolved into the pure isomers byknown methods, for example by recrystallisation from a solvent, bychromatography, for example high pressure liquid chromatography (HPLC)on acetylcellulose, with the aid of suitable microorganisms, by cleavagewith specific, immobilised enzymes, or via the formation of inclusioncompounds, for example using crown ethers, only one isomer beingcomplexed.

Apart from the separation of corresponding mixtures of isomers, purediasteroisomers can be obtained according to the invention also bygenerally known methods of stereoselective synthesis, for example bycarrying out the process according to the invention using startingmaterials having correspondingly suitable stereochemistry.

In each case it is advantageous to isolate or synthesize thebiologically more active isomer, where the individual components havedifferent biological activity.

The compounds of formula (I) may also be obtained in the form of theirhydrates and/or may include other solvents, for example solvents whichmay have been used for the crystallisation of compounds in solid form.

The invention relates to all those embodiments of the process accordingto which a compound obtainable as starting material or intermediate atany stage of the process is used as starting material and all or some ofthe remaining steps are carried out, or in which a starting material isused in the form of a derivative and/or a salt and/or its diastereomers,or, especially, is formed under the reaction conditions. For instancecompounds of formula (I) bearing a functional group in its free orprotected form can be used as starting materials for the preparation offurther compounds of formula (I). For such manipulations methods knownto the person skilled in the art can be applied.

In the processes of the present invention it is preferable to use thosestarting materials and intermediates which result in the compounds offormula (I) that are especially preferred.

The invention relates especially to the preparation processes describedin the Examples.

In the area of pest control, the compounds of formula (I) according tothe invention are active ingredients exhibiting valuable preventiveand/or curative activity with a very advantageous biocidal spectrum anda very broad spectrum, even at low rates of concentration, while beingwell tolerated by warm-blooded animals, fish and plants. They are,surprisingly, equally suitable for controlling both plant pests andecto- and endo-parasites in humans and more especially in productivelivestock, domestic animals and pets. They are effective against all orindividual development stages of normally sensitive animal pests, butalso of resistant animal pests, such as insects and representatives ofthe order Acarina, nematodes, cestodes and trematodes, while at the sametime protecting useful organisms. The insecticidal or acaricidalactivity of the active ingredients according to the invention maymanifest itself directly, i.e. in the mortality of the pests, whichoccurs immediately or only after some time, for example during moulting,or indirectly, for example in reduced oviposition and/or hatching rate.Good activity corresponds to a mortality of at least 50 to 60%.

Successful control within the scope of the subject of the invention ispossible, in particular, of pests from the orders Lepidoptera,Coleoptera, Orthoptera, Isoptera, Psocoptera, Anoplura, Mallophaga,Thysanoptera, Heteroptera, Homoptera, Hymenoptera, Diptera,Siphonaptera, Thysanura and Acarina, mainly Acarina, Diptera,Thysanoptera, Lepidoptera and Coleoptera. Very especially good controlis possible of the following pests:

Abagrotisi spp., Abraxas spp., Acantholeucania spp., Acanthoplusia spp.,Acarus spp., Acarus siro, Aceria spp., Aceria sheldoni, Acleris spp.,Acoloithus spp., Acompsia spp., Acossus spp., Acria spp., Acrobasisspp., Acrocercops spp., Acrolepia spp., Acrolepiopsis spp., Acronictaspp., Acropolitis spp., Actebia spp., Aculus spp., Aculusschlechtendali, Adoxophyes spp., Adoxophyes reticulana, Aedes spp.,Aegeria spp., Aethes spp., Agapeta spp., Agonopterix spp., Agriopisspp., Agriotes spp., Agriphila spp., Agrochola spp., Agroperina spp.,Alabama spp., Alabama argillaceae, Agrotis spp., Albuna spp., Alcathoespp., Alcis spp., Aleimma spp., Aletia spp., Aleurothrixus spp.,Aleurothrixus floccosus, Aleyrodes spp., Aleyrodes brassicae, Allophyesspp., Alsophila spp., Amata spp., Amathes spp., Amblyomma spp.,Amblyptilia spp., Ammoconia spp., Amorbia spp., Amphion spp., Amphipoeaspp., Amphipyra spp., Amyelois spp., Anacamptodes spp., Anagrapha spp.,Anarsia spp., Anatrychyntis spp., Anavitrinella spp., Ancylis spp.,Andropolia spp., Anhimella spp., Antheraea spp., Antherigona spp.,Antherigona soccata, Anthonomus spp., Anthonomus grandis, Anticarsiaspp., Anticarsia gemmatalis, Aonidiella spp., Apamea spp., Aphania spp.,Aphelia spp., Aphididae, Aphisspp., Apotomis spp., Aproaerema spp.,Archippus spp., Archips spp., Acromyrmex, Arctia spp., Argas spp.,Argolamprotes spp., Argyresthia spp., Argyrogramma spp., Argyroplocespp., Argyrotaenia spp., Arotrophora spp., Ascotis spp., Aspidiotusspp., Aspilapteryx spp., Asthenoptycha spp., Aterpia spp., Athetis spp.,Atomaria spp., Atomaria linearis, Atta spp., Atypha spp., Autographaspp., Axylia spp., Bactra spp., Barbara spp., Batrachedra spp.,Battaristis spp., Bembecia spp., Bemisia spp., Bemisia tabaci, Bibiospp., Bibio hortulanis, Bisigna spp., Blastesthia spp., Blatta spp.,Blatella spp., Blepharosis spp., Bleptina spp., Boarmia spp., Bombyxspp., Bomolocha spp., Boophilus spp., Brachmia spp., Bradina spp.,Brevipalpus spp., Brithys spp., Bryobia spp., Bryobia praetiosa,Bryotropha spp., Bupalus spp., Busseola spp., Busseola fusca, Caberaspp., Cacoecimorpha spp., Cadra spp., Cadra cautella, Caenurgina spp.,Calipitrimerus spp., Callierges spp., Callophpora spp., Callophporaerythrocephala, Calophasia spp., Caloptilia spp., Calybites spp.,Capnoptycha spp., Capua spp., Caradrina spp., Caripeta spp., Carmentaspp., Carposina spp., Carposina nipponensis, Catamacta spp., Catelaphrisspp., Catoptria spp., Caustoloma spp., Celaena spp., Celypha spp.,Cenopis spp., Cephus spp., Ceramica spp., Cerapteryx spp., Ceratitisspp, Ceratophyllus spp., Ceroplaster spp., Chaetocnema spp., Chaetocnematibialis, Chamaesphecia spp., Charanvca spp., Cheimophila spp.,Chersotis spp., Chiasmia spp., Chilo spp., Chionodes spp., Chorioptesspp., Choristoneura spp., Chrysaspidia spp., Chrysodeixis spp.,Chrysomya spp., Chrysomphalus spp., Chrysomphalus dictyospermi,Chrysomphalus aonidium, Chrysoteuchia spp., Cilix spp., Cimex spp.,Clysia spp., Clysia ambiguelia, Clepsis spp., Cnaemidophorus spp.,Cnaphalocrocis spp., Cnephasia spp., Coccus spp., Coccus hesperidum,Cochylis spp., Coleophora spp., Colotois spp., Commophila spp., Conistraspp., Conopomorpha spp., Corcyra spp., Comutiplusia spp., Cosmia spp.,Cosmopolites spp., Cosmopterix spp., Cossus spp., Costaeonvexa spp.,Crambus spp., Creatonotos spp., Crocidolomia spp., Crocidolomiabinotalis, Croesia spp., Crymodes spp., Cryptaspasma spp., Cryptoblabesspp., Cryptocala spp., Cryptophlebia spp., Cryptophlebia leucotreta,Cryptoptila spp., Ctenopseustis spp., Ctenocephalides spp., Cuculliaspp., Curcullo spp., Culex spp., Cuterebra spp., Cydia spp., Cydiapomonella, Cymbalophora spp., Dactylethra spp., Dacus spp., Dadica spp.,Damalinea spp., Dasychira spp., Decadarchis spp., Decodes spp.,Deilephila spp., Deltodes spp., Dendrolimus spp., Depressaria spp.,Dermestes spp., Dermanyssus spp., Dermanyssus gallinae, Diabrotica spp.,Diachrysia spp., Diaphania spp., Diarsia spp., Diasemia spp., Diatraeaspp., Diceratura spp., Dichomeris spp., Dichrocrocis spp., Dichroramphaspp., Dicycla spp., Dioryctria spp., Diparopsis spp., Diparopsiscastanea, Dipleurina spp., Diprion spp., Diprionidae, Discestra spp.,Distantiella spp., Distantiella theobroma, Ditula spp., Diurnea spp.,Doratopteryx spp., Drepana spp., Drosphila spp., Drosphila melanogaster,Dysauxes spp., Dysdercus spp., Dysstroma spp., Eana spp., Earias spp.,Ecclitica spp., Ecdytolopha spp., Ecpyrrhorrhoe spp., Ectomyelois spp.,Eetropis spp., Egira spp., Elasmopalpus spp., Emmelia spp., mpoascaspp., Empyreuma spp., Enargia spp., Enarmonia spp., Endopiza spp.,Endothenia spp., Endotricha spp., Eoreuma spp., Eotetranychus spp.,Eotetranychus carpini, Epagoge spp., Epelis spp., Ephestia spp.,Ephestiodes spp., Epiblema spp., Epiehoristodes spp., Epinotia spp.,Epiphyas spp., Epiplema spp., Epipsestis spp., Epirrhoe spp., Episimusspp., Epitymbia spp., Epllachna spp., Erannis spp., Erastria spp.,Eremnus spp., Ereunetis spp., Eriophyes spp., Eriosoma spp., Eriosomalanigerum, Erythroneura spp., Estigmene spp., Ethmia spp., Etiella spp.,Euagrotis spp., Eucosma spp., Euehlaena spp., Euelidia spp., Eueosmaspp., Euchistus spp., Eucosmomorpha spp., Eudonia spp., Eufidonia spp.,Euhyponomeutoides spp., Eulepitodes spp., Eulia spp., Eulithis spp.,Eupithecia spp., Euplexia spp., Eupoecilia spp., Eupoecilia ambiguella,Euproctis spp., Eupsilia spp., Eurhodope spp., Eurois spp., Eurygasterspp., Eurythmia spp., Eustrotia spp., Euxoa spp., Euzophera spp.,Evergestis spp., Evippe spp., Exartema spp., Fannia spp., Faronta spp.,Feltia spp., Filatima spp., Fishia spp., Frankliniella spp., Fumibotysspp., Gaesa spp., Gasgardia spp., Gastrophilus spp., Gelechia spp.,Gilpinia spp., Gilpinia polytoma, Glossina spp., Glyphipterix spp.,Glyphodes spp., Gnorimoschemini spp., Gonodonta spp., Gortyna spp.,Gracillaria spp., Graphania spp., Grapholita spp., Grapholitha spp.,Gravitarmata spp., Gretchena spp., Griselda spp., Gryllotalpa spp.,Gynaephora spp., Gypsonoma spp., Hada spp., Haematopinus spp.,Halisidota spp., Harpipteryx spp., Harrisina spp., Hedya spp.,Helicoverpa spp., Heliophobus spp., Heliothis spp., Hellula spp.,Helotropa spp., Hemaris spp., Hercinothrips spp., Herculia spp.,Hermonassa spp., Heterogenea spp., Holomelina spp., Homadaula spp.,Homoeosoma spp., Homogiaea spp., Homohadena spp., Homona spp.,Homonopsis spp., Hoplocampa spp., Hoplodrina spp., Hoshinoa spp.,Hxalomma spp., Hydraecia spp., Hydriomena spp., Hyles spp., Hyloicusspp., Hypagyrtis spp., Hypatima spp., Hyphantria spp., Hyphantria cunea,Hypocala spp., Hypocoena spp., Hypodema spp., Hyppobosca spp., Hypsipylaspp., Hyssia spp., Hysterosia spp., Idaea spp., Idia spp., Ipimorphaspp., Isia spp., Isochorista spp., Isophrictis spp., Isopolia spp.,Isotrias spp., Ixodes spp., Itame spp., Jodia spp., Jodis spp., Kawabeaspp., Keiferia spp., Keiferia lycopersicella, Labdia spp., Lacinipoliaspp., Lambdina spp., Lamprothritpa spp., Laodelphax spp., Lasius spp.,Laspeyresia spp., Leptinotarsa spp., Leptinotarsa decemlineata,Leptocorisa spp., Leptostales spp., Lecanium spp., Lecanium comi,Lepidosaphes spp., Lepisma spp., Lepisma saccharina, Lesmone spp.,Leucania spp., Leucinodes spp., Leucophaea spp., Leucophaea maderae,Leucoptera spp., Leucoptera scitelia, Linognathus spp., Liposcelis spp.,Lissorhoptrus spp., Lithacodia spp., Lithocolletis spp., Lithomoia spp.,Lithophane spp., Lixodessa spp., Lobesia spp., Lobesia botrana,Lobophora spp., Locusta spp., Lomanaltes spp., Lomographa spp.,Loxagrotis spp., Loxostege spp., Lucilia spp., Lymantria spp., Lymnaeciaspp., Lyonetia spp., Lyriomyza spp., Macdonnoughia spp., Macrauzataspp., Macronoctua spp., Macrosiphus spp., Malacosoma spp., Maliarphaspp., Mamestra spp., Mamestra brassicae, Manduca spp., Manduca sexta,Marasmia spp., Margaritia spp., Matratinea spp., Matsumuraeses spp.,Melanagromyza spp., Melipotes spp., Melissopus spp., Melittia spp.,Melolontha spp., Meristis spp., Meritastis spp., Merophyas spp.,Mesapamea spp., Mesogona spp., Mesoleuca spp., Metanema spp.,Metendothenia spp., Metzneria spp., Micardia spp., Microcorses spp.,Microleon spp., Mnesictena spp., Mocis spp., Monima spp., Monochroaspp., Monomorium spp., Monomorium pharaonis, Monopsis spp., Morrisoniaspp., Musca spp., Mutuuraia spp., Myelois spp., Mythimna spp., Myzusspp., Naranga spp., Nedra spp., Nemapogon spp., Neodiprion spp.,Neosphaleroptera spp., Nephelodes spp., Nephotettix spp., Nezara spp.,Nilaparvata spp., Niphonympha spp., Nippoptilia spp., Noctua spp., Nolaspp., Notocelia spp., Notodonta spp., Nudaurelia spp., Ochropleura spp.,Ocnerostoma spp., Oestrus spp., Olethreutes spp., Oligia spp., Olindiaspp., Olygonychus spp., Olygonychus gallinae, Oncocnemis spp.,Operophtera spp., Ophisma spp., Opogona spp., Oraesia spp., Orniodorosspp., Orgyia spp., Oria spp., Orseolia spp., Orthodes spp., Orthogoniaspp., Orthosia spp., Oryzaephilus spp., Oscinella spp., Oscinella frit,Osminia spp., Ostrinia spp., Ostrinia nubilalis, Otiorhynchus spp.,Ourapteryx spp., Pachetra spp., Pachysphinx spp., Pagyda spp.,Paleacrita spp., Paliga spp., Palthis spp., Pammene spp., Pandemis spp.,Panemeria spp., Panolis spp., Panolis flammea, Panonychus spp.,Parargyresthia spp., Paradiarsia spp., Paralobesia spp., Paranthrenespp., Parapandemis spp., Parapediasia spp., Parastichtis spp.,Parasyndemis spp., Paratoria spp., Pareromeme spp., Pectinophora spp.,Pectinophora gossypiella, Pediculus spp., Pegomyia spp., Pegomyiahyoscyami, Pelochrista spp., Pennisetia spp., Penstemonia spp.,Pemphigus spp., Peribatodes spp., Peridroma spp., Perileucoptera spp.,Periplaneta spp., Perizoma spp., Petrova spp., Pexicopia spp., Phaloniaspp., Phalonidia spp., Phaneta spp., Phlyctaenia spp., Phlyctinus spp.,Phorbia spp., Phragmatobia spp., Phricanthes spp., Phthorimaea spp.,Phthorimaea operculella, Phyllocnistis spp., Phyllocoptruta spp.,Phyllocoptruta oleivora, Phyllonorycter spp., Phyllophila spp.,Phylloxera spp., Pieris spp., Pieris rapae, Piesma spp., Planococusspp., Planotortrix spp., Platyedra spp., Platynota spp., Platyptiliaspp., Platysenta spp., Plodia spp., Plusia spp., Plutella spp., Plutellaxylostella, Podosesia spp., Polia spp., Popilliaspp., Polymixis spp.,Polyphagotarsonemus spp., Polyphagotarsonemus latus, Prays spp.,Prionoxystus spp., Probole spp., Proceras spp., Prochoerodes spp.,Proeulia spp., Proschistis spp., Proselena spp., Proserpinus spp.,Protagrotis spp., Proteoteras spp., Protobathra spp., Protoschinia spp.,Pselnophorus spp., Pseudaletia spp., Pseudanthonomus spp.,Pseudaternelia spp., Pseudaulacaspis spp., Pseudexentera spp.,Pseudococus spp., Pseudohermenias spp., Pseudoplusia spp., Psoroptesspp., Psylla spp., Psylliodes spp., Pterophorus spp., Ptycholoma spp.,Pulvinaria spp., Pulvinaria aethiopica, Pyralis spp., Pyrausta spp.,Pyrgotis spp., Pyrreferra spp., Pyrrharctia spp., Quadraspidiotus spp.,Rancora spp., Raphia spp., Reticultermes spp., Retinia spp., Rhagoletisspp, Rhagoletis pomonella, Rhipicephalus spp., Rhizoglyphus spp.,Rhizopertha spp., Rhodnius spp., Rhophalosiphum spp., Rhopobota spp.,Rhyacia spp., Rhyacionia spp., Rhynchopacha spp., Rhyzosthenes spp.,Rivula spp., Rondotia spp., Rusidrina spp., Rynchaglaea spp., Sabulodesspp., Sahlbergella spp., Sahlbergella singularis, Saissetia spp., Samiaspp., Sannina spp., Sanninoidea spp., Saphoideus spp., Sarcoptes spp.,Sathrobrota spp., Scarabeidae, Sceliodes spp., Schinia spp.,Schistocerca spp., Schizaphis spp., Schizura spp., Schreckensteiniaspp., Sciara spp., Scirpophaga spp., Scirthrips auranti, Scoparia spp.,Scopula spp., Scotia spp., Scotinophara spp., Scotogramma spp.,Scrobipalpa spp., Scrobipalpopsis spp., Semiothisa spp., Sereda spp.,Sesamiaspp., Sesia spp., Sicya spp., Sideridis spp., Simyra spp.,Sineugraphe spp., Sitochroa spp., Sitobion spp., Sitophilus spp.,Sitotroga spp., Solenopsis spp., Smerinthus spp., Sophronia spp.,Spaelotis spp., Spargaloma spp., Sparganothis spp., Spatalistis spp.,Sperchia spp., Sphecia spp., Sphinx spp., Spilonota spp., Spodopteraspp., Spodoptera littoralis, Stagmatophora spp., Staphylinochrous spp.,Stathmopoda spp., Stenodes spp., Sterrha spp., Stomoxys spp., Strophedraspp., Sunira spp., Sutyna spp., Swammerdamia spp., Syllomatia spp.,Sympistis spp., Synanthedon spp., Synaxis spp., Syncopacma spp.,Syndemis spp., Syngrapha spp., Synthomeida spp., Tabanus spp.,Taeniarchis spp., Taeniothrips spp., Tannia spp., Tarsonemus spp.,Tegulifera spp., Tehama spp., Teleiodes spp., Telorta spp., Tenebriospp., Tephrina spp., Teratoglaea spp., Terricula spp., Tethea spp.,Tetranychus spp., Thalpophila spp., Thaumetopoea spp., Thiodia spp.,Thrips spp., Thrips palmi, Thrips tabaci, Thyridopteryx spp., Thyrisspp., Tineola spp., Tipula spp., Tortricidia spp., Tortrix spp., Tracheaspp., Trialeurodes spp., Trialeurodes vaporariorum, Triatoma spp.,Triaxomera spp., Tribolium spp., Tricodectes spp., Trichoplusia spp.,Trichoplusia ni, Trichoptilus spp., Trioza spp., Trioza erytreae,Triphaenia spp., Triphosa spp., Trogoderma spp., Tyria spp., Udea spp.,Unaspis spp., Unaspis citri, Utetheisa spp., Valeriodes spp., Vespaspp., Vespamima spp., Vitacea spp., Vitula spp., Witlesia spp., Xanthiaspp., Xanthorhoe spp., Xanthotype spp., Xenomicta spp., Xenopsylla spp.,Xenopsylla cheopsis, Xestia spp., Xylena spp., Xylomyges spp., Xyrosarisspp., Yponomeuta spp., Ypsolopha spp., Zale spp., Zanclognathus spp.,Zeiraphera spp., Zenodoxus spp., Zeuzera spp., Zygaena spp.,

It is also possible to control pests of the class Nematoda using thecompounds according to the invention. Such pests include, for example,

root knot nematodes, cyst-forming nematodes and also stem and leafnematodes;

especially of Heterodera spp., e.g. Heterodera schachtii, Heterodoraavenae and Heterodora trifolii; Globodera spp., e.g. Globoderarostochiensis; Meloidogyne spp., e.g. Meloidogyne incognita andMeloidogyne javanica; Radopholus spp., e.g. Radopholus similis;Pratylenchus, e.g. Pratylenchus neglectans and Pratylenchus penetrans;Tylenchulus, e.g. Tylenchulus semipenetrans; Longidorus, Trichodorus,Xiphinema, Ditylenchus, Apheenchoides and Anguina; especiallyMeloidogyne, e.g. Meloidogyne incognita, and Heterodera, e.g. Heteroderaglycines.

An especially important aspect of the present invention is the use ofthe compounds of formula (I) according to the invention in theprotection of plants against parasitic feeding pests.

The action of the compounds according to the invention and thecompositions comprising them against animal pests can be significantlybroadened and adapted to the given circumstances by the addition ofother insecticides, acaricides or nematicides. Suitable additivesinclude, for example, representatives of the following classes of activeingredient: organophosphorus compounds, nitrophenols and derivatives,formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons,neonicotinoids and Bacillus thuringiensis preparations.

Examples of especially suitable mixing partners include: azamethiphos;chlorfenvinphos; cypermethrin, cypermethrin high-cis; cyromazine;diafenthiuron; diazinon; dichlorvos; dicrotophos; dicyclanil;fenoxycarb; fluazuron; furathiocarb; isazofos; iodfenphos; kinoprene;lufenuron; methacriphos; methidathion; monocrotophos; phosphamidon;profenofos; diofenolan; a compound obtainable from the Bacillusthuringiensis strain GC91 or from strain NCTC11821; pymetrozine;bromopropylate; methoprene; disulfoton; quinalphos; tau-fluvalinate;thiocyclam; thiometon; aldicarb; azinphos-methyl; benfuracarb;bifenthrin; buprofezin; carbofuran; dibutylaminothio; cartap;chlorfluazuron; chlorpyrifos; clothianidin; cyfluthrin;lambda-cyhalothrin; alpha-cypermethrin; zeta-cypermethrin; deltamethrin;diflubenzuron; endosulfan; ethiofencarb; fenitrothion; fenobucarb;fenvalerate; formothion; methiocarb; heptenophos; imidacloprid;isoprocarb; methamidophos; methomyl; mevinphos; parathion;parathion-methyl; phosalone; pirimicarb; propoxur; teflubenzuron;terbufos; triazamate; fenobucarb; tebufenozide; fipronil;beta-cyfluthrin; silafluofen; fenpyroximate; pyridaben; pyridalyl;fenazaquin; pyriproxyfen; pyrimidifen; nitenpyram; acetamiprid;emamectin; emamectin-benzoate; spinosad; a plant extract that is activeagainst insects; a preparation that comprises nematodes and is activeagainst insects; a preparation obtainable from Bacillus subtilis; apreparation that comprises fungi and is active against insects; apreparation that comprises viruses and is active against insects;chlorfenapyr; acephate; acrinathrin; alanycarb; alphamethrin; amitraz;AZ 60541; azinphos A; azinphos M; azocyclotin; bendiocarb; bensultap;beta-cyfluthrin; brofenprox; bromophos A; bufencarb; butocarboxin;butylpyridaben; cadusafos; carbaryl; carbophenothion; chloethocarb;chlorethoxyfos; chlormephos; cis-resmethrin; clocythrin; clofentezine;cyanophos; cycloprothrin; cyhexatin; demeton M; demeton S;demeton-S-methyl; dichlofenthion; dicliphos; diethion; dimethoate;dimethylvinphos; dinotefuran; dioxathion; edifenphos; esfenvalerate;ethion; ethofenprox; ethoprophos; etrimphos; fenamiphos; fenbutatinoxide; fenothiocarb; fenpropathrin; fenpyrad; fenthion; fluazinam;flucycloxuron; flucythrinate; flufenoxuron; flufenprox; fonophos;fosthiazate; fubfenprox; HCH; hexaflumuron; hexythiazox; flonicamid;iprobenfos; isofenphos; isoxathion; ivermectin; malathion; mecarbam;mesulfenphos; metaldehyde; metolcarb; milbemectin; moxidectin; naled; NC184; nithiazine; omethoate; oxamyl; oxydemethon M; oxydeprofos;permethrin; phenthoate; phorate; phosmet; phoxim; pirimiphos M;pirimiphos E; promecarb; propaphos; prothiofos; prothoate; pyrachlophos;pyradaphenthion; pyresmethrin; pyrethrum; tebufenozide; salithion;sebufos; sulfotep; sulprofos; tebufenpyrad; tebupirimphos; tefluthrin;temephos; terbam; tetrachlorvinphos; thiacloprid; thiafenox;thiamethoxam; thiodicarb; thiofanox; thionazin; thuringiensin;tralomethrin; triarathene; triazophos; triazuron; trichlorfon;triflumuron; trimethacarb; vamidothion; xylylcarb; etoxazole;zetamethrin; indoxacarb; methoxyfenozide; bifenazate; XMC (3,5-xylylmethylcarbamate); or the fungus pathogen Metarhizium anisopliae.

The compounds according to the invention can be used to control, i.e. toinhibit or destroy, pests of the mentioned type occurring on plants,especially on useful plants and ornamentals in agriculture, inhorticulture and in forestry, or on parts of such plants, such as thefruits, blossoms, leaves, stems, tubers or roots, while in some casesplant parts that grow later are still protected against those pests.

Target crops include especially cereals, such as wheat, barley, rye,oats, rice, maize and sorghum; beet, such as sugar beet and fodder beet;fruit, e.g. pomes, stone fruit and soft fruit, such as apples, pears,plums, peaches, almonds, cherries and berries, e.g. strawberries,raspberries and blackberries; leguminous plants, such as beans, lentils,peas and soybeans; oil plants, such as rape, mustard, poppy, olives,sunflowers, coconut, castor oil, cocoa and groundnuts; cucurbitaceae,such as marrows, cucumbers and melons; fibre plants, such as cotton,flax, hemp and jute; citrus fruits, such as oranges, lemons, grapefruitand mandarins; vegetables, such as spinach, lettuce, asparagus,cabbages, carrots, onions, tomatoes, potatoes and paprika; lauraceae,such as avocado, cinnamon and camphor; and tobacco, nuts, coffee,aubergines, sugar cane, tea, pepper, vines, hops, bananas, naturalrubber plants and ornamentals.

Further areas of use of the compounds according to the invention are theprotection of stored goods and storerooms and the protection of rawmaterials, and also in the hygiene sector, especially the protection ofdomestic animals and productive livestock against pests of the mentionedtype, more especially the protection of domestic animals, especiallycats and dogs, from infestation by fleas, ticks and nematodes.

The invention therefore relates also to pesticidal compositions, such asemulsifiable concentrates, suspension concentrates, directly sprayableor dilutable solutions, spreadable pastes, dilute emulsions, wettablepowders, soluble powders, dispersible powders, wettable powders, dusts,granules and encapsulations of polymer substances, that comprise atleast one of the compounds according to the invention, the choice offormulation being made in accordance with the intended objectives andthe prevailing circumstances.

The active ingredient is used in those compositions in pure form, asolid active ingredient, for example, in a specific particle size, orpreferably together with at least one of the adjuvants customary informulation technology, such as extenders, e.g. solvents or solidcarriers, or surface-active compounds (surfactants). In the area ofparasite control in humans, domestic animals, productive livestock andpets it will be self-evident that only physiologically tolerableadditives are used.

Solvents are, for example: non-hydrogenated or partly hydrogenatedaromatic hydrocarbons, preferably fractions C₈ to C₁₂ of alkylbenzenes,such as xylene mixtures, alkylated naphthalenes ortetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such asparaffins or cyclohexane, alcohols, such as ethanol, propanol orbutanol, glycols and ethers and esters thereof, such as propyleneglycol, dipropylene glycol ether, ethylene glycol or ethylene glycolmonomethyl or -ethyl ether, ketones, such as cyclohexanone, isophoroneor diacetone alcohol, strongly polar solvents, such asN-methylpyrrolid-2-one, dimethyl sulfoxide or N,N-dimethylformamide,water, non-epoxidized or epoxidized plant oils, such as non-epoxidizedor epoxidized rapeseed, castor, coconut or soya oil, and silicone oils.

The solid carriers used, for example for dusts and dispersible powders,are as a rule natural rock powders, such as calcite, talc, kaolin,montmorillonite or attapulgite. Highly disperse silicic acids or highlydisperse absorbent polymers can also be added to improve the physicalproperties. Granular adsorptive granule carriers are porous types, suchas pumice, crushed brick, sepiolite or bentonite, and non-sorbentcarrier materials are calcite or sand. A large number of granularmaterials of inorganic or organic nature can furthermore be used, inparticular dolomite or comminuted plant residues.

Surface-active compounds are, depending on the nature of the activecompound to be formulated, nonionic, cationic and/or anionic surfactantsor surfactant mixtures with good emulsifying, dispersing and wettingproperties. The surfactants listed below are to be regarded only asexamples; many other surfactants which are customary in formulationtechnology and are suitable according to the invention are described inthe relevant literature.

Nonionic surfactants are, in particular, polyglycol ether derivatives ofaliphatic or cycloaliphatic alcohols, saturated or unsaturated fattyacids and alkylphenols, which can contain 3 to 30 glycol ether groupsand 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to18 carbon atoms in the alkyl radical of the alkylphenols. Substanceswhich are furthermore suitable are water-soluble polyethylene oxideadducts, containing 20 to 250 ethylene glycol ether and 10 to 100propylene glycol ether groups, on propylene glycol, ethylenediaminopolypropylene glycol and alkyl polypropylene glycol having 1 to10 carbon atoms in the alkyl chain. The compounds mentioned usuallycontain 1 to 5 ethylene glycol units per propylene glycol unit. Examplesare nonylphenol-polyethoxyethanols, castor oil polyglycol ethers,polypropylene-polyethylene oxide adducts,tributylphenoxypoly-ethoxyethanol, polyethylene glycol andoctylphenoxypolyethoxyethanol. Other substances are fatty acid esters ofpolyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.

The cationic surfactants are, in particular, quaternary ammonium saltswhich contain, as substituents, at least one alkyl radical having 8 to22 C atoms and, as further substituents, lower, non-halogenated orhalogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts arepreferably in the form of halides, methyl-sulfates or ethyl-sulfates.Examples are stearyltrimethyl-ammonium chloride andbenzyl-di-(2-chloroethyl)-ethyl-ammonium bromide.

Suitable anionic surfactants can be both water-soluble soaps andwater-soluble synthetic surface-active compounds. Suitable soaps are thealkali metal, alkaline earth metal and substituted or unsubstitutedammonium salts of higher fatty acids (C₁₀-C₂₂), such as the sodium orpotassium salts of oleic or stearic acid, or of naturally occurringfatty acid mixtures, which can be obtained, for example, from coconutoil or tall oil; and furthermore also the fatty acid methyltaurinesalts. However, synthetic surfactants are more frequently used, inparticular fatty sulfonates, fatty sulfates, sulfonated benzimidazolederivatives or alkylarylsulfonates. The fatty sulfonates and sulfatesare as a rule in the form of alkali metal, alkaline earth metal orsubstituted or unsubstituted-ammonium salts and in general have an alkylradical of 8 to 22 C atoms, alkyl also including the alkyl moiety ofacyl radicals; examples are the sodium or calcium salt of ligninsulfonicacid, of dodecylsulfuric acid ester or of a fatty alcohol sulfatemixture prepared from naturally occurring fatty acids. These alsoinclude the salts of sulfuric acid esters and sulfonic acids of fattyalcohol-ethylene oxide adducts. The sulfonated benzimidazole derivativespreferably contain 2 sulfonic acid groups and a fatty acid radicalhaving about 8 to 22 C atoms. Alkylarylsulfonates are, for example, thesodium, calcium or triethanolammonium salts of dodecylbenzenesulfonicacid, of dibutylnaphthalenesulfonic acid or of a naphthalenesulfonicacid-formaldehyde condensation product. Corresponding phosphates, suchas salts of the phosphoric acid ester of a p-nonylphenol-(4-14)-ethyleneoxide adduct or phospholipids, can further also be used.

The compositions as a rule comprise 0.1 to 99%, in particular 0.1 to95%, of active compound and 1 to 99.9%, in particular 5 to 99.9%, of—atleast—one solid or liquid auxiliary, it being possible as a rule for 0to 25%, in particular 0.1 to 20%, of the composition to be surfactants(% is in each case percent by weight). While concentrated compositionsare more preferred as commercial goods, the end user as a rule usesdilute compositions which comprise considerably lower concentrations ofactive compound. Preferred compositions are composed, in particular, asfollows (%=percent by weight):

Emulsifiable Concentrates:

active ingredient: 1 to 90%, preferably 5 to 20% surfactant: 1 to 30%,preferably 10 to 20% solvent: 5 to 98%, preferably 70 to 85%Dusts:

active ingredient: 0.1 to 10%, preferably 0.1 to 1% solid carrier: 99.9to 90%, preferably 99.9 to 99%Suspension Concentrates:

active ingredient: 5 to 75%, preferably 10 to 50% water: 94 to 24%,preferably 88 to 30% surfactant: 1 to 40%, preferably 2 to 30%Wettable Powders:

active ingredient: 0.5 to 90%, preferably 1 to 80% surfactant: 0.5 to20%, preferably 1 to 15% solid carrier: 5 to 99%, preferably 15 to 98%Granules:

active ingredient: 0.5 to 30%, preferably 3 to 15% solid carrier: 99.5to 70%, preferably 97 to 85%

The compositions according to the invention may also comprise furthersolid or liquid adjuvants, such as stabilisers, e.g. vegetable oils orepoxidised vegetable oils (e.g. epoxidised coconut oil, rapeseed oil orsoybean oil), antifoams, e.g. silicone oil, preservatives, viscosityregulators, binders and/or tackifiers as well as fertilisers or otheractive ingredients for obtaining special effects, e.g. acaricides,bactericides, fungicides, nematicides, molluscicides or selectiveherbicides.

The crop protection products according to the invention are prepared inknown manner, in the absence of adjuvants, e.g. by grinding, sievingand/or compressing a solid active ingredient or mixture of activeingredients, for example to a certain particle size, and in the presenceof at least one adjuvant, for example by intimately mixing and/orgrinding the active ingredient or mixture of active ingredients with theadjuvant(s). The invention relates likewise to those processses for thepreparation of the compositions according to the invention and to theuse of the compounds of formula (I) in the preparation of thosecompositions.

The invention relates also to the methods of application of the cropprotection products, i.e. the methods of controlling pests of thementioned type, such as spraying, atomising, dusting, coating, dressing,scattering or pouring, which are selected in accordance with theintended objectives and the prevailing circumstances, and to the use ofthe compositions for controlling pests of the mentioned type. Typicalrates of concentration are from 0.1 to 1000 ppm, preferably from 0.1 to500 ppm, of active ingredient. The rates of application per hectare aregenerally from 1 to 2000 g of active ingredient per hectare, especiallyfrom 10 to 1000 g/ha, preferably from 20 to 600 g/ha, more especiallyfrom 20 to 100 g/ha.

A preferred method of application in the area of crop protection isapplication to the foliage of the plants (foliar application), thefrequency and the rate of application being dependent upon the risk ofinfestation by the pest in question. However, the active ingredient canalso penetrate the plants through the roots (systemic action) when thelocus of the plants is impregnated with a liquid formulation or when theactive ingredient is incorporated in solid form into the locus of theplants, for example into the soil, e.g. in granular form (soilapplication). In the case of paddy rice crops, such granules may beapplied in metered amounts to the flooded rice field.

The crop protection products according to the invention are alsosuitable for protecting plant propagation material, e.g. seed, such asfruits, tubers or grains, or plant cuttings, against animal pests. Thepropagation material can be treated with the composition beforeplanting: seed, for example, can be dressed before being sown. Theactive ingredients according to the invention can also be applied tograins (coating), either by impregnating the seeds in a liquidformulation or by coating them with a solid formulation. The compositioncan also be applied to the planting site when the propagation materialis being planted, for example to the seed furrow during sowing. Theinvention relates also to such methods of treating plant propagationmaterial and to the plant propagation material so treated.

The following Examples serve to illustrate the invention. They do notlimit the invention. Temperatures are given in degrees Celsius; mixingratios of solvents are given in parts by volume. In the examples, TBDMSis t-butyl-dimethylsilyl

PREPARATION EXAMPLES Example A2.14″-Desoxy-4″-(S)-phtalimidooxy-avermectin B₁

Step A: 1.0 g of 5-OTBDMS-4″-desoxy-avermectinB₁-4″-(R)-trifluoromethanesulfonate and 0.44 g of N-hydroxyphtalimide isdissolved in 20 ml acetonitrile. The solution is cooled to 0° C. then0.2 ml of 1,8-diazabicyclo[5.4.0]undec-7-ene in 2 ml acetonitrile areadded dropwise over 15 min. The reaction mixture is stirred at roomtemperature for 3 hours, diluted with ethyl acetate, washed withsaturated ammonium chloride, water and brine. The organic phase is driedover sodium sulfate, and concentrated in vacuo. The residue is purifiedby flash-chromatography (silica gel hexane/ethyl acetate 8/2) providing5-OTBDMS-4″-desoxy-4″-(S)-phtalimidooxy-avermectin B₁ which ischaracterized by its mass and NMR spectra.

Step B: To a solution of 0.54 g of5-OTBDMS-4″-desoxy-4″-(S)-phtalimidooxy-avermectin B₁ in 10 mltetrahydrofuran is added 2 ml of a HF-pyridine solution (consisting of25 g 70% HF-Pyridin, 27,5 ml tetrahydrofuran and 12,5 ml pyridine), andthe mixture is stirred at room temperature for 24 hours, poured intowater, extracted with ethyl acetate; the organic phase is washed withsaturated sodium bicarbonate, dried over sodium sulfate, andconcentrated in vacuo. The residue is purified by flash-chromatography(silica gel hexane/ethyl acetate 6/4) providing4″-desoxy-4″-(S)-phtalimidooxy-avermectin B₁ which is characterized byits mass and NMR spectra.

Example A4.1 4″-Desoxy-4″-(R)-phtalimidooxy-avermectin B₁

Step A: 1.0 g of 5-OTBDMS-4″-desoxy-avermectinB₁-4″-(S)-trifluoromethanesulfonate and 0.44 g of N-hydroxyphtalimide isdissolved in 20 ml acetonitrile. The solution is cooled to 0° C. then0.2 ml of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in 2 ml acetonitrileare added dropwise over 15 min. The reaction mixture is stirred at roomtemperature for 3 hours, diluted with ethyl acetate, washed withsaturated ammonium chloride, water and brine. The organic phase is driedover sodium sulfate, and concentrated in vacuo. The residue is purifiedby flash-chromatography (silica gel hexane/ethyl acetate 85/15)providing 5-OTBDMS-4″-desoxy-4″-(R)-phtalimidooxy-avermectin B₁ which ischaracterized by its mass and NMR spectra.

Step B: To a solution of 0.54 g of5-OTBDMS-4″-desoxy-4″-(R)-phtalimidooxy-avermectin B₁ in 10 mltetrahydrofuran is added 2 ml of a HF-pyridine solution (consisting of25 g 70% HF-Pyridin, 27.5 ml tetrahydrofuran and 12.5 ml pyridine), andthe mixture is stirred at room temperature for 24 hours, poured intowater, extracted with ethyl acetate; the organic phase is washed withsaturated sodium bicarbonate, dried over sodium sulfate, andconcentrated in vacuo. The residue is purified by flash-chromatography(silica gel hexane/ethyl acetate 6/4) providing4″-desoxy-4″-(R)-phtalimidooxy-avermectin B₁ which is characterized byits mass and NMR spectra.

Example A2.2 4″-desoxy-4′-(S)-aminooxy-avermectin B₁

To a solution of 0.4 g of 4″-desoxy-4″-(S)-phtalimidooxy-avermectin B₁(example A2.1) in 7 ml ethanol is added 30 mg of hydrazine monohydrate.The reaction mixture is stirred at room temperature for 1 hour, pouredinto water, extracted with ethyl acetate, the organic phase is washedwith water, saturated sodium bicarbonated, dried over sodium sulfate andconcentrated in vacuo, yielding 4″-desoxy-4″-(S)-aminooxy-avermectin B₁which is characterized by its mass and NMR spectra.

Example A4.2 4″-desoxy-4″-(R)-aminooxy-avermectin B₁

To a solution of 0.15 g of 4″-desoxy-4″-(R)-phtalimidooxy-avermectin B₁(example A2.1) in 5 ml ethanol is added 11 mg of hydrazine monohydrate.The reaction mixture is stirred at room temperature for 1 hour, pouredinto water, extracted with ethyl acetate; the organic phase is washedwith water, saturated sodium bicarbonated, dried over sodium sulfate andconcentrated in vacuo, yielding 4″-desoxy-4″-(R)-aminooxy-avermectin B₁,which is characterized by its mass and NMR spectra.

Example A1.1 4″-Desoxy-4″-(S)-(ethylideneamino)oxy-avermectin B₁

To a solution of 0.1 g of 4″-desoxy-4″-(S)-aminooxy-avermectin B₁(example A2.2) in 5 ml toluene is added 25 mg acetaldehyde. The reactionmixture is stirred at room temperature for 1 hour and concentrated invacuo, yielding 4″-desoxy-4″-(S)-[(ethylidene)amino]oxy-avermectin B₁which is characterized by its mass and NMR spectra.

Example A1.24″-Desoxy-4″-(S)-[(3-hydroxy-ethylidene)amino]oxy-avermectin B₁

To a solution of 0.1 g of 4″-desoxy-4″-(S)-aminooxy-avermectin B₁(example A2.2) in 5 ml toluene are added 3 mg of pyridinium para-toluenesulfonate and 10 mg of glycolaldehyde. The reaction mixture is stirredat room temperature for 1 hour, poured into water, extracted with ethylacetate, dried over sodium sulfate and concentrated in vacuo, yielding4″-desoxy-4″-(S)-[(3-hydroxy-ethylidene)amino]oxy-avermectin B₁ which ischaracterized by its mass and NMR spectra.

Example A1.13 4″-Desoxy-4″-(S)-(cyclopentylideneamino)oxy-avermectin B₁

To a solution of 0.1 g of 4″-desoxy-4″-(S)-aminooxy-avermectin B₁(example A2.2) in 5 ml toluene are added 3 mg of pyridinium para-toluenesulfonate and 13 mg of cyclopentanone. The reaction mixture is stirredat room temperature for 1 hour, poured into water, extracted with ethylacetate, dried over sodium sulfate and concentrated in vacuo, yielding4″-desoxy-4″-(S)-(cyclopentylideneamino)oxy-avermectin B₁ which ischaracterized by its mass and NMR spectra.

Example A1.16 D-Fructose, 4″-O-(avermectin B₁)oxime

To a solution of 0.1 g of 4″-desoxy-4″-(S)-aminoxy-avermectin B₁(example A2.2) in 5 ml dioxan and 0.05 ml water is added 28 mg ofpyridinium para-toluene sulfonate and 202 mg of D-Fructose. The reactionmixture is stirred at room temperature for 24 hours, poured into water,extracted with ethyl acetate, dried over sodium sulfate and concentratedin vacuo, yielding D-Fructose, 4″-O-(avermectin B₁)oxime which ischaracterized by its mass and NMR spectra.

Example A2.3 4″-Desoxy-4″-(S)-(acetylamino)oxy-avermectin B₁

Step A: To a solution of 6 g of5-OTBDMS-4″-desoxy-4″-(S)-phtalimidooxy-avermectin B₁ (example A2.1,step A) in 100 ml ethanol is added 0.39 ml of hydrazine monohydrate. Thereaction mixture is stirred at room temperature for 1 hour, poured intowater, extracted with ethyl acetate; the organic phase is washed withsaturated sodium bicarbonate, dried over sodium sulfate and sulfate andconcentrated in vacuo, yielding5-OTBDMS-4″-desoxy-4″-(S)-aminooxy-avermectin B₁.

Step B: To a solution of 0.2 g of5-OTBDMS-4″-desoxy-4″-(S)-aminooxy-avermectin B₁ and 0.03 ml pyridine in5 ml dichloromethane at 0° C. is added 0.02 ml acetyl chloride. Thereaction mixture is stirred at 0° C. for 1 hour, poured into water,extracted with dichloromethane, dried over sodium sulfate andconcentrated in vacuo. To a solution of the crude residue in 1.5 mltetrahydrofuran is is added 0.3 ml of a HF-pyridine solution (consistingof 25 g 70% HF-Pyridine, 27.5 ml tetrahydrofuran and 12.5 ml pyridine),and the mixture is stirred at room temperature for 12 hours, poured intowater, extracted with ethyl acetate; the organic phase is washed withsaturated sodium bicarbonate, dried over sodium sulfate, andconcentrated in vacuo, yielding4″-desoxy-4″-(S)-(acetylamino)oxy-avermectin B₁ which is characterizedby its mass and NMR spectra.

Example A2.11 4″-Desoxy-4″-(S)-[(methoxycarbonyl)amino]oxy-avermectin B₁

To a stirred solution of 0.2 g of 4″-desoxy-4″-(S)-aminooxy-avermectinB₁ (example A2.2) in 3 ml ethyl acetate and 3 ml sodium bicarbonate isadded 24 mg of methyl chloroformate. The reaction mixture is stirred atroom temperature for 5 hours, diluted with ethyl acetate, washed withbrine, dried over sodium sulfate and concentrated in vacuo. The residueis purified by flash-chromatography (silica gel hexane/ethyl acetate65/35) providing 4″-desoxy-4″-(S)-[(methoxycarbonyl)amino]oxy-avermectinB₁ which is characterized by its mass and NMR spectra.

Example A1.17 4″-desoxy-4″-(S)-[(methylidene)amino]oxy-avermectin B₁

To a solution of 2.62 g of 4″-desoxy-4″-(S)-aminooxy-avermectin B₁(example A2.2) in 25 ml tetrahydrofuran is added 4.84 ml of aqueousformaldehyde (36%). The reaction mixture is stirred at room temperaturefor 2.5 hours and concentrated in vacuo, yielding4″-desoxy-4″-(S)-[(methylidene)amino]oxy-avermectin B₁ which ischaracterized by its mass and NMR spectra.

Example A2.13 4″-desoxy-4″-(S)-(methylamino)oxy-avermectin B₁

To a solution of 2.78 g of4″-desoxy-4″-(S)-[(methylidene)amino]oxy-avermectin B₁ (example A1.17)in 50 ml toluene is added 25 ml of a solution ofdiisobutylaluminium-hydride in toluene (1.2 mol/l) under nitrogen.During the addition, the reaction flask is cooled in a water bath, thetemperature of the reaction mixture is kept below 25° C. Then thereaction mixture is stirred at room temperature for 3 hours, extractedwith ethyl acetate and aqueous sodium tartrate, dried over sodiumsulfate and concentrated in vacuo. The residue is purified bychromatography on silica gel with hexane/ethyl acetate, yielding4″-desoxy-4″-(S)(methylamino)oxy-avermectin B1 which is characterized byits mass and NMR spectra.

Similarly to the preparation examples above it is also possible toprepare the compounds listed in Tables A1 to A8 and Tables 1 to 48. Inthe Tables, the symbol

denotes, where necessary, the bond through which the radical in questionis attached to the the skeleton.

Since in most cases the compounds are present as mixtures of theavermectin derivatives B1a and B1b, characterization by customaryphysical data such as melting point or refractive index makes littlesense. For this reason, the compounds are characterized by the retentiontimes which are determined in an analysis by HPLC (high performanceliquid chromatography). Here, the term B1a refers to the main componentin which R₁ is sec-butyl, with a content of usually more than 80%. B1bdenotes the minor component in which R₁ is isopropyl. Where tworetention times are given for the B1a or the B1b derivative or both thecompounds are mixtures of diastereomers which can be separatedchromatographically. In the case of compounds where a retention time isgiven only in column B1a or only in column B1b, the pure B1a or B1bcomponent, respectively, can be obtained during work-up. The correctstructures of the B1a and B1b components are assigned by massspectrometry.

The following method is used for HPLC analysis:

HPLC gradient conditions Solvent A: 0.01% of trifluoroacetic acid in H₂OSolvent B: 0.01% of trifluoroacetic acid in CH₃CN Flow rate Time [min] A[%] B [%] [μl/min] 0 80 20 500 0.1 50 50 500 10 5 95 500 15 0 100 500 170 100 500 17.1 80 20 500 22 80 20 500 Type of column YMC-Pack ODS-AQColumn length 125 mm Internal diameter of  2 mm column: Temperature 40°C.

The YMC-Pack ODS-AQ column used for the chromatography of the compoundsis manufactured by YMC, Alte Raesfelderstrasse 6, 46514 Schermbeck,Germany.

TABLE A1 Compounds of the formula (I) in which R₁ is sec-butyl (B1a) orisopropyl (B1b)

Retention time (min) No. R₄ R₅ B1a B1b A1.1  Methyl H 11.09 A1.2 

H  8.96  8.21 A1.3  Ethyl H 11.18 10.51 A1.4 

H 10.98 10.34 A1.5  CCl₃ H 12.31 A1.6  cyclopropyl H 11.00 10.35 A1.7 COOH H  5.19 A1.8  Phenyl H 12.69 A1.9 

H  9.16 A1.10

H  6.57  5.97 A1.11

H  5.28  4.84 A1.12 methyl methyl 11.63 A1.13 —(CH₂)₄— 12.33 11.59 A1.14

 7.99 A1.15

methyl  5.61  5.26 A1.16

 6.01 A1.17 H H 11.27 10.57 A1.18

methyl  5.17 5.04  4.75 A1.19

methyl 11.90 11.15 A1.20

methyl 13.3513.21 12.9312.79 A1.21

methyl 11.96 11.21 A1.22 —(CH₂)₂—O—(CH₂)₂— 12.89 12.38 A1.23—(CH₂)₂—N(CH₃)—(CH₂)₂—  5.16  4.72

TABLE A2 Compounds of the formula (I) in which R₁ is sec-butyl (B1a) orisopropyl (B1b).

Retention time (min) No. R₂ R₃ B1a B1b A2.1 

A2.2  H H 5.16 4.28 A2.3 

H 7.90 7.22 A2.4 

H 8.28 7.63 A2.5 

H 9.31 8.56 A2.7 

H 8.34 7.64 A2.8 

H 8.86 8.14 A2.9 

H 8.70 8.00 A2.10

H 8.45 7.75 A2.11

H 7.91 7.21 A2.12

H 8.09 7.41 A2.13

H 7.80 7.15 A2.14 H methyl 8.00 7.31 A2.15

H 8.16 8.96 A2.16

methyl A2.17

methyl A2.18

methyl A2.19 methyl methyl 12.05  11.36 

TABLE A3 Compounds of the formula (I) in which R₁ is sec-butyl (B1a) orisopropyl (B1b).

Retention time (min) No. R₄ R₅ B1a B1b A3.1  Methyl H A3.2 

H A3.3  Ethyl H A3.4 

H A3.5  CCl₃ H A3.6  cyclopropyl H A3.7  COOH H A3.8  Phenyl H A3.9 

H A3.10

H A3.11

H A3.12 methyl methyl A3.13 —(CH₂)₄— A3.14

A3.15

methyl A3.16

TABLE A4 Compounds of the formula (I) in which R₁ is sec-butyl orisopropyl

Retention time (min) No. R₂ R₃ B1a B1b A4.1

9.98 A4.2 H H 8.76 8.10

TABLE A5 Compounds of the formula (I) in which R₁ is sec-butyl (B1a) orisopropyl (B1b)

Retention time (min) No. R₄ R₅ B1a B1b A5.1  Methyl H A5.2 

H  8.05 A5.3  Ethyl H A5.4 

H A5.5  cyclopropyl H A5.6  COOH H  8.48 A5.7  Phenyl H 12.12 A5.8 

H A5.9  methyl methyl 10.77 A5.10 —(CH₂)₄— 11.41 A5.11

 7.20 A5.12

methyl A5.13 —(CH₂)₂—N(CH₃)—(CH₂)₂—  5.32 A5.14 —(CH₂)₂—O—(CH₂)₂— 10.24A5.15 CH₃(CH₂)₂CH(CH₃)— H 13.01 A5.16 (CH₃CH₂)₂CH— H 12.91 A5.17n-pentyl H 12.91 A5.18

H 10.40 A5.19 —(CH₂)₃— 10.88 A5.20 —(CH₂)₅— 12.21 A5.21

H  9.13 A5.22

methyl  8.37 A5.23

methyl  9.02 A5.24

methyl  5.28 A5.25

methyl 10.88 A5.26

methyl 11.84 A5.27

methyl 12.01 A5.28 F₃C— methyl 11.79 A5.29 ethyl ethyl 12.71 A5.30

H 12.98 A5.31

H 14.19 A5.32

 5.87 A5.33 H H

TABLE A6 Compounds of the formula (I) in which R₁ is sec-butyl (B1a) orisopropyl (B1b).

Retention time (min) No. R₂ R₃ B1a B1b A6.1 

11.50 A6.2  H H  5.51 A6.3 

H  7.57 A6.4 

H A6.5 

H A6.6 

H  8.14 A6.7 

H  8.80 A6.8 

H A6.9 

H A6.10

H A6.11

H A6.12

H A6.13

H A6.14

H  8.64 A6.15 methyl H A6.16

methyl A6.17

methyl A6.18

methyl

TABLE A7 Compounds of the formula (I) in which R₁ is sec-butyl (B1a) orisopropyl (B1b).

Retention time (min) No. R₄ R₅ B1a B1b A7.1 Methyl H A7.2

H A7.3 Ethyl H A7.4

H A7.5 CCl₃ H A7.6 cyclopropyl H A7.7 COOH H A7.8 Phenyl H A7.9 methylmethyl  A7.10 —(CH₂)₄—

TABLE A8 Compounds of the formula (I) in which R₁ is sec-butyl (B1a) orisopropyl (B1b).

Retention time (min) No. R₂ R₃ B1a B1b A8.1

A8.2 H H

TABLE B Compounds of the formula (IA)

and of the formula (IB)

wherein the combination of R₂ and R₃ holds for compound (IA) and thecombination of R₄ and R₅ holds for compound (IB): R₂ or R₄ R₃ or R₅ B.1 H H B.2  Methyl H B.3  Ethyl H B.4  n-propyl H B.5  iso-propyl H B.6 n-butyl H B.7  s-butyl H B.8  iso-butyl H B.9  t-butyl H B.10 CH₃(CH₂)₂CH(CH₃)— H B.11  (CH₃CH₂)₂CH— H B.12  n-pentyl H B.13 CH₂═CH—CH₂— H B.14  CH₃—CH═CH—CH₂— H B.15  HO—CH₂— H B.16  HO—CH₂—CH₂— HB.17  CH₃—CH(OH)— H B.18  (CH₃)₂C(OH)— H B.19  HO—CH₂—CH₂—CH₂— H B.20 HO—CH₂—CH₂—CH₂—CH₂— H B.21  CH₃—O—CH₂— H B.22  CH₃—O—CH₂—CH₂— H B.23 CH₃—CH₂—O—CH₂— H B.24  CH₃—CH₂—O—CH₂—CH₂— H B.25  (CH₃O)₂CH— H B.26 NH₂—CH₂— H B.27  CF₃— H B.28  CH₂F H B.29  CHF₂ H B.30  CH₂Cl H B.31 CHCl₂ H B.32  CCl₃ H B.33  CN H B.34  Phenyl H B.35  Benzyl H B.36 

H B.37 

H B.38 

H B.39 

H B.40 

H B.41 

H B.42 

H B.43 

H B.44 

H B.45 

H B.46 

H B.47  pyrid-2-yl H B.48  pyrid-3-yl H B.49  pyrid-4-yl H B.50 

H B.51 

H B.52 

H B.53 

H B.54 

H B.55 

H B.56 

H B.57 

H B.58 

H B.59 

H B.60 

H B.61 

H B.62 

H B.63 

H B.64 

H B.65  benzoyl H B.66 

H B.67 

H B.68 

H B.69 

H B.70 

H B.71 

H B.72  SO₂Me H B.73  SO₂Et H B.74  ethyl methyl B.75  CH₂OH methylB.76  2-hydroxyethyl methyl B.77  methoxymethyl methyl B.78 methylthiomethyl methyl B.79  CF₃ methyl B.80  CH₃—CHCl— methyl B.81 CH₂═CH—CH₂— methyl B.82  phenyl methyl B.83 

methyl B.84 

methyl B.85 

methyl B.86 

methyl B.87 

methyl B.88 

methyl B.89 

methyl B.90 

methyl B.91 

methyl B.92 

methyl B.93 

methyl B.94 

methyl B.95  H ethyl B.96  H n-propyl B.97  H iso-propyl B.98  H n-butylB.99  H s-butyl B.100 H iso-butyl B.101 H t-butyl B.102 HCH₃(CH₂)₂CH(CH₃)— B.103 H (CH₃CH₂)₂CH— B.104 H n-pentyl B.105 HCH₂═CH—CH₂— B.106 H CH₃—CH═CH—CH₂— B.107 H HO—CH₂— B.108 H HO—CH₂—CH₂—B.109 H CH₃—CH(OH)— B.110 H (CH₃)₂C(OH)— B.111 H HO—CH₂—CH₂—CH₂— B.112 HHO—CH₂—CH₂—CH₂—CH₂— B.113 H CH₃—O—CH₂— B.114 H CH₃—O—CH₂—CH₂— B.115 HCH₃—CH₂—O—CH₂— B.116 H CH₃—CH₂—O—CH₂—CH₂— B.117 H (CH₃O)₂CH— B.118 HNH₂—CH₂— B.119 H CF₃— B.120 H CH₂F B.121 H CHF₂ B.122 H CH₂Cl B.123 HCHCl₂ B.124 H CCl₃ B.125 H CN B.126 H phenyl B.127 H Benzyl B.128 H

B.129 H

B.130 H

B.131 H

B.132 H 4-F-phenyl B.133 H 4-Cl-phenyl B.134 H

B.135 H 4-Br-phenyl B.136 H

B.137 H

B.138 H

B.139 H pyrid-2-yl B.140 H pyrid-3-yl B.141 H pyrid-4-yl B.142 H

B.143 H

B.144 H

B.145 H

B.146 H

B.147 H

B.148 H

B.149 H

B.150 H

B.151 H

B.152 H

B.153 H

B.154 H

B.155 H

B.156 H

B.157 H benzoyl B.158 H

B.159 H

B.160 H

B.161 H

B.162 H

B.163 H

B.164 H SO₂Me B.165 H SO₂Et B.166 methyl ethyl B.167 methyl CH₂═CH—CH₂—B.168 methyl phenyl B.169 methyl hydroxymethyl B.170 methyl2-hydroxyethyl B.171 methyl methoxymethyl B.172 methyl methylthiomethylB.173 methyl CF₃ B.174 methyl CH₃—CHCl— B.175 methyl benzyl B.176 methyl

B.177 methyl

B.178 methyl

B.179 methyl

B.180 methyl

B.181 methyl

B.182 methyl benzoyl B.183 methyl

B.184 methyl

B.185 methyl

B.186 methyl

B.187 methyl —CN B.188 methyl methyl B.189 ethyl ethyl B.190hydroxymethyl ethyl B.191 hydroxymethyl CH₂═CH—CH₂— B.192 hydroxymethyl

B.193 hydroxymethyl

B.194 hydroxymethyl

B.195 hydroxymethyl

B.196 hydroxymethyl —CN B.197 —CH₂—CH₂═CH₂ ethyl B.198

ethyl B.199

ethyl B.200

ethyl B.201

ethyl B.202 CH₂═CH—CH₂— CH₂═CH—CH₂— B.203 CH₂═CH—CH₂—

B.204 CH₂═CH—CH₂—

B.205 CH₂═CH—CH₂—

B.206 CH₂═CH—CH₂—

B.207 CH₂═CH—CH₂— —CN B.208

CH₂═CH—CH₂— B.209

CH₂═CH—CH₂— B.210

CH₂═CH—CH₂— B.211

CH₂═CH—CH₂— B.212 —CH₂—CH₂—CH₂— B.213 —CH₂—CH═CH— B.214

B.215

B.216

B.217

B.218

B.219

B.220

B.221

B.222

B.223

B.224

B.225

B.226

B.227

B.228

B.229

B.230

B.231

B.232

B.233

B.234

B.235

B.236

B.237

B.238

B.239

B.240

B.241

B.242

B.243

B.244

B.245

B.246

B.247

B.248

B.249

Table 1: A compound of the formula (IA) in which the configuration atthe ε-position is S, n is 1, A-B is —CH═CH—, R₁ is sec-butyl orisopropyl and the combination of R₂ and R₃ for each compoundscorresponds to a line B.1 to B.249 of Table B.

Table 2: A compound of the formula (IA) in which the configuration atthe ε-position is S, n is 1, A-B is —CH₂—CH₂—, R₁ is sec-butyl orisopropyl and the combination of R₂ and R₃ for each compoundscorresponds to a line B.1 to B.249 of Table B.

Table 3: A compound of the formula (IA) in which the configuration atthe ε-position is S, n is 0, A-B is —CH═CH—, R₁ is sec-butyl orisopropyl and the combination of R₂ and R₃ for each compoundscorresponds to a line B.1 to B.249 of Table B.

Table 4: A compound of the formula (IA) in which the configuration atthe ε-position is S, n is 0, A-B is —CH₂—CH₂—, R₁ is sec-butyl orisopropyl and the combination of R₂ and R₃ for each compoundscorresponds to a line B.1 to B.249 of Table B.

Table 5: A compound of the formula (IA) in which the configuration atthe ε-position is R, n is 1, A-B is —CH═CH—, R₁ is sec-butyl orisopropyl and the combination of R₂ and R₃ for each compoundscorresponds to a line B.1 to B.249 of Table B.

Table 6: A compound of the formula (IA) in which the configuration atthe ε-position is R, n is 1, A-B is —CH₂—CH₂—, R₁ is sec-butyl orisopropyl and the combination of R₂ and R₃ for each compoundscorresponds to a line B.1 to B.249 of Table B.

Table 7: A compound of the formula (IA) in which the configuration atthe ε-position is R, n is 0, A-B is —CH═CH—, R₁ is sec-butyl orisopropyl and the combination of R₂ and R₃ for each compoundscorresponds to a line B.1 to B.249 of Table B.

Table 8: A compound of the formula (IA) in which the configuration atthe ε-position is R, n is 0, A-B is —CH₂—CH₂—, R₁ is sec-butyl orisopropyl and the combination of R₂ and R₃ for each compoundscorresponds to a line B.1 to B.249 of Table B.

Table 9: A compound of the formula (IB) in which the configuration atthe ε-position is S, n is 1, A-B is —CH═CH—, R₁ is sec-butyl orisopropyl and the combination of R₄ and R₅ for each compoundscorresponds to a line B.1 to B.249 of Table B.

Table 10: A compound of the formula (IB) in which the configuration atthe ε-position is S, n is 1, A-B is —CH₂—CH₂—, R₁ is sec-butyl orisopropyl and the combination of R₄ and R₅ for each compoundscorresponds to a line B.1 to B.249 of Table B.

Table 11: A compound of the formula (IB) in which the configuration atthe ε-position is S, n is 0, A-B is —CH═CH—, R₁ is sec-butyl orisopropyl and the combination of R₄ and R₅ for each compoundscorresponds to a line B.1 to B.249 of Table B.

Table 12: A compound of the formula (IB) in which the configuration atthe ε-position is S, n is 0, A-B is —CH₂—CH₂—, R₁ is sec-butyl orisopropyl and the combination of R₄ and R₅ for each compoundscorresponds to a line B.1 to B.249 of Table B.

Table 13: A compound of the formula (IB) in which the configuration atthe ε-position is R, n is 1, A-B is —CH═CH—, R₁ is sec-butyl orisopropyl and the combination of R₄ and R₅ for each compoundscorresponds to a line B.1 to B.249 of Table B.

Table 14: A compound of the formula (IB) in which the configuration atthe ε-position is R, n is 1, A-B is —CH₂—CH₂—, R₁ is sec-butyl orisopropyl and the combination of R₄ and R₅ for each compoundscorresponds to a line B.1 to B.249 of Table B.

Table 15: A compound of the formula (IB) in which the configuration atthe ε-position is R, n is 0, A-B is —CH═CH—, R₁ is sec-butyl orisopropyl and the combination of R₄ and R₅ for each compoundscorresponds to a line B.1 to B.249 of Table B.

Table 16: A compound of the formula (IB) in which the configuration atthe ε-position is R, n is 0, A-B is —CH₂—CH₂—, R₁ is sec-butyl orisopropyl and the combination of R₄ and R₅ for each compoundscorresponds to a line B.1 to B.249 of Table B.

Table 17: A compound of the formula (IA) in which the configuration atthe ε-position is S, n is 1, A-B is —CH═CH—, R₁ is cyclohexyl and thecombination of R₂ and R₃ for each compounds corresponds to a line B.1 toB.249 of Table B.

Table 18: A compound of the formula (IA) in which the configuration atthe ε-position is S, n is 1, A-B is —CH₂—CH₂—, R₁ is cyclohexyl and thecombination of R₂ and R₃ for each compounds corresponds to a line B.1 toB.249 of Table B.

Table 19: A compound of the formula (IA) in which the configuration atthe ε-position is S, n is 0, A-B is —CH═CH—, R₁ is cyclohexyl and thecombination of R₂ and R₃ for each compounds corresponds to a line B.1 toB.249 of Table B.

Table 20: A compound of the formula (IA) in which the configuration atthe ε-position is S, n is 0, A-B is —CH₂—CH₂—, R₁ is cyclohexyl and thecombination of R₂ and R₃ for each compounds corresponds to a line B.1 toB.249 of Table B.

Table 21: A compound of the formula (IA) in which the configuration atthe ε-position is R, n is 1, A-B is —CH═CH—, R₁ is cyclohexyl and thecombination of R₂ and R₃ for each compounds corresponds to a line B.1 toB.249 of Table B.

Table 22: A compound of the formula (IA) in which the configuration atthe ε-position is R, n is 1, A-B is —CH₂—CH₂—, R₁ is cyclohexyl and thecombination of R₂ and R₃ for each compounds corresponds to a line B.1 toB.249 of Table B.

Table 23: A compound of the formula (IA) in which the configuration atthe ε-position is R, n is 0, A-B is —CH═CH—, R₁ is cyclohexyl and thecombination of R₂ and R₃ for each compounds corresponds to a line B.1 toB.249 of Table B.

Table 24: A compound of the formula (IA) in which the configuration atthe ε-position is R, n is 0, A-B is —CH₂—CH₂—, R₁ is cyclohexyl and thecombination of R₂ and R₃ for each compounds corresponds to a line B.1 toB.249 of Table B.

Table 25: A compound of the formula (IB) in which the configuration atthe ε-position is S, n is 1, A-B is —CH═CH—, R₁ is cyclohexyl and thecombination of R₄ and R₅ for each compounds corresponds to a line B.1 toB.249 of Table B.

Table 26: A compound of the formula (IB) in which the configuration atthe ε-position is S, n is 1, A-B is —CH₂—CH₂—, R₁ is cyclohexyl and thecombination of R₄ and R₅ for each compounds corresponds to a line B.1 toB.249 of Table B.

Table 27: A compound of the formula (IB) in which the configuration atthe ε-position is S, n is 0, A-B is —CH═CH—, R₁ is cyclohexyl and thecombination of R₄ and R₅ for each compounds corresponds to a line B.1 toB.249 of Table B.

Table 28: A compound of the formula (IB) in which the configuration atthe ε-position is S, n is 0, A-B is —CH₂—CH₂—, R₁ is cyclohexyl and thecombination of R₄ and R₅ for each compounds corresponds to a line B.1 toB.249 of Table B.

Table 29: A compound of the formula (IB) in which the configuration atthe ε-position is R, n is 1, A-B is —CH═CH—, R₁ is cyclohexyl and thecombination of R₄ and R₅ for each compounds corresponds to a line B.1 toB.249 of Table B.

Table 30: A compound of the formula (IB) in which the configuration atthe ε-position is R, n is 1, A-B is —CH₂—CH₂—, R₁ is cyclohexyl and thecombination of R₄ and R₅ for each compounds corresponds to a line B.1 toB.249 of Table B.

Table 31: A compound of the formula (IB) in which the configuration atthe ε-position is R, n is 0, A-B is —CH═CH—, R₁ is cyclohexyl and thecombination of R₄ and R₅ for each compounds corresponds to a line B.1 toB.249 of Table B.

Table 32: A compound of the formula (IB) in which the configuration atthe ε-position is R, n is 0, A-B is —CH₂—CH₂—, R₁ is cyclohexyl and thecombination of R₄ and R₅ for each compounds corresponds to a line B.1 toB.249 of Table B.

Table 33: A compound of the formula (IA) in which the configuration atthe ε-position is S, n is 1, A-B is —CH═CH—, R₁ is 1-methyl-butyl andthe combination of R₂ and R₃ for each compounds corresponds to a lineB.1 to B.249 of Table B.

Table 34: A compound of the formula (IA) in which the configuration atthe ε-position is S, n is 1, A-B is —CH₂—CH₂—, R₁ is 1-methyl-butyl andthe combination of R₂ and R₃ for each compounds corresponds to a lineB.1 to B.249 of Table B.

Table 35: A compound of the formula (IA) in which the configuration atthe ε-position is S, n is 0, A-B is —CH═CH—, R₁ is 1-methyl-butyl andthe combination of R₂ and R₃ for each compounds corresponds to a lineB.1 to B.249 of Table B.

Table 36: A compound of the formula (IA) in which the configuration atthe ε-position is S, n is 0, A-B is —CH₂—CH₂—, R₁ is 1-methyl-butyl andthe combination of R₂ and R₃ for each compounds corresponds to a lineB.1 to B.249 of Table B.

Table 37: A compound of the formula (IA) in which the configuration atthe ε-position is R, n is 1, A-B is —CH═CH—, R₁ is 1-methyl-butyl andthe combination of R₂ and R₃ for each compounds corresponds to a lineB.1 to B.249 of Table B.

Table 38: A compound of the formula (IA) in which the configuration atthe ε-position is R, n is 1, A-B is —CH₂—CH₂—, R₁ is 1-methyl-butyl andthe combination of R₂ and R₃ for each compounds corresponds to a lineB.1 to B.249 of Table B.

Table 39: A compound of the formula (IA) in which the configuration atthe ε-position is R, n is 0, A-B is —CH═CH—, R₁ is 1-methyl-butyl andthe combination of R₂ and R₃ for each compounds corresponds to a lineB.1 to B.249 of Table B.

Table 40: A compound of the formula (IA) in which the configuration atthe ε-position is R, n is 0, A-B is —CH₂—CH₂—, R₁ is 1-methyl-butyl andthe combination of R₂ and R₃ for each compounds corresponds to a lineB.1 to B.249 of Table B.

Table 41: A compound of the formula (IB) in which the configuration atthe ε-position is S, n is 1, A-B is —CH═CH—, R₁ is 1-methyl-butyl andthe combination of R₄ and R₅ for each compounds corresponds to a lineB.1 to B.249 of Table B.

Table 42: A compound of the formula (IB) in which the configuration atthe ε-position is S, n is 1, A-B is —CH₂—CH₂—, R₁ is 1-methyl-butyl andthe combination of R₄ and R₅ for each compounds corresponds to a lineB.1 to B.249 of Table B.

Table 43: A compound of the formula (IB) in which the configuration atthe ε-position is S, n is 0, A-B is —CH═CH—, R₁ is 1-methyl-butyl andthe combination of R₄ and R₅ for each compounds corresponds to a lineB.1 to B.249 of Table B.

Table 44: A compound of the formula (IB) in which the configuration atthe ε-position is S, n is 0, A-B is —CH₂—CH₂—, R₁ is 1-methyl-butyl andthe combination of R₄ and R₅ for each compounds corresponds to a lineB.1 to B.249 of Table B.

Table 45: A compound of the formula (IB) in which the configuration atthe ε-position is R, n is 1, A-B is —CH═CH—, R₁ is 1-methyl-butyl andthe combination of R₄ and R₅ for each compounds corresponds to a lineB.1 to B.249 of Table B.

Table 46: A compound of the formula (IB) in which the configuration atthe ε-position is R, n is 1, A-B is —CH₂—CH₂—, R₁ is 1-methyl-butyl andthe combination of R₄ and R₅ for each compounds corresponds to a lineB.1 to B.249 of Table B.

Table 47: A compound of the formula (IB) in which the configuration atthe ε-position is R, n is 0, A-B is —CH═CH—, R₁ is 1-methyl-butyl andthe combination of R₄ and R₅ for each compounds corresponds to a lineB.1 to B.249 of Table B.

Table 48: A compound of the formula (IB) in which the configuration atthe ε-position is R, n is 0, A-B is —CH₂—CH₂—, R₁ is 1-methyl-butyl andthe combination of R₄ and R₅ for each compounds corresponds to a lineB.1 to B.249 of Table B.

Formulation examples for use in crop protection (%=percent by weight)

EXAMPLE F1 Emulsion concentrates a) b) c) Active compound 25% 40% 50%Calcium dodecylbenzenesulphonate  5%  8%  6% Castor oil polyethyleneglycol ether  5% — — (36 mol of EO) Tributylphenol polyethylene glycolether — 12%  4% (30 mol of EO) Cyclohexanone — 15% 20% Xylene mixture65% 25% 20%Mixing of finely ground active compound and additives gives an emulsionconcentrate which, by dilution with water, affords emulsions of thedesired concentration.

EXAMPLE F2 Solutions a) b) c) d) active ingredient 80% 10%  5% 95%ethylene glycol monomethyl ether — 20% — — polyethylene glycol (MW 400)— 70% — — N-methylpyrrolid-2-one 20% — — — epoxidised coconut oil — — 1%  5% petroleum ether (boiling range: 160-190° C.) — — 94% —Mixing of finely ground active compound and additives gives a solutionsuitable for use in the form of microdrops.

EXAMPLE F3 Granules a) b) c) d) Active compound 5% 10%  8% 21% Kaolin94%  — 79% 54% Finely divided silicic acid 1% — 13%  7% Attapulgite —90% — 18%The active compound is dissolved in dichloromethane, the solution issprayed onto the mixture of carriers and the solvent is evaporated underreduced pressure.

EXAMPLE F4 Wettable powder a) b) c) Active compound 25% 50% 75% Sodiumlignosulphonate  5%  5% — Sodium lauryl sulphate  3% —  5% Sodiumdiisobutylnaphthalene sulphonate —  6% 10% Octylphenol polyethyleneglycol ether —  2% — (7-8 mol of EO) Finely divided silicic acid  5% 10%10% Kaolin 62% 27% —Active compound and additives are mixed and the mixture is ground in asuitable mill. This gives wettable powders which can be diluted withwater to give suspensions of the desired concentration.

EXAMPLE F5 Emulsion concentrate Active compound 10% Octylphenolpolyethylene glycol ether (4–5 mol of EO)  3% Calciumdodecylbenzenesulphonate  3% Castor oil polyethylene glycol ether (36mol of EO)  4% Cyclohexanone 30% Xylene mixture 50%Mixing of finely ground active compound and additives gives an emulsionconcentrate which, by dilution with water, affords emulsions of thedesired concentration.

EXAMPLE F6 Extruder granules Active compound 10% Sodium lignosulphonate 2% Carboxymethylcellulose  1% Kaolin 87%Active compound and additives are mixed, the mixture is ground,moistened with water, extruded and granulated, and the granules aredried in a stream of air.

EXAMPLE 7 Coated granules Active compound 3% Polyethylene glycol (MW200) 3% Kaolin 94% In a mixer, the finely ground active compound is applied uniformly tothe kaolin which has been moistened with polyethylene glycol. This givesdust-free coated granules.

EXAMPLE F8 Suspension concentrate Active compound 40% Ethylene glycol10% Nonylphenol polyethylene glycol ether (15 mol of EO)  6% Sodiumlignosulphonate 10% Carboxymethylcellulose  1% Aqueous formaldehydesolution (37%) 0.2%  Aqueous silicone oil emulsion (75%) 0.8%  Water 32%Mixing of finely ground active compound and additives gives a suspensionconcentrate which, by dilution with water, affords suspensions of thedesired concentration.

BIOLOGICAL EXAMPLES Example B1 Activity Against Spodoptera littoralis

Young soya bean plants are sprayed with an aqueous emulsion spray liquorwhich comprises 12.5 ppm of active compound, and, after the spraycoating has dried on, populated with 10 caterpillars of the first stageof Spodoptera littoralis and introduced into a plastic container. 3 dayslater, the reduction in the population in percent and the reduction inthe feeding damage in percent (% activity) are determined by comparingthe number of dead caterpillars and the feeding damage between thetreated and the untreated plants.

In this test, the compounds of the Tables A1 to A4 and Tables 1 to 48show good activity. Thus, in particular the compounds A1.1 to A4.2 aremore than 80% effective.

Example B2 Activity Against Spodoptera littoralis, Systemic

Maize seedlings are placed into the test solution which comprises 12.5ppm of active compound. After 6 days, the leaves are cut off, placedonto moist filter paper in a Petri dish and populated with 12 to 15Spodoptera littoralis larvae of the L₁ stage. 4 days later, thereduction of the population in percent (% activity) is determined bycomparing the number of dead caterpillars between the treated and theuntreated plants.

In this test, the compounds of the Tables A1 to A4 and Tables 1 to 48show good activity. Thus, in particular the compounds A1.1 to A4.2 aremore than 80% effective.

Example B3 Activity Against Heliothis virescens

30-35 eggs of Heliothis virescens which are 0- to 24-hour-old are placedonto filter paper in a Petri dish on a layer of synthetic feed. 0.8 mlof the test solution which comprises 12.5 ppm of active compound is thenpipetted onto the filter papers. Evaluation is carried out after 6 days.The reduction in the population in percent (% activity) is determined bycomparing the number of dead eggs and larvae on the treated and theuntreated filter papers.

In this test, the compounds of the Tables A1 to A4 and Tables 1 to 48show good activity. Thus, in particular the compounds A1.1 to A4.2 aremore than 80% effective.

Example B4 Activity Against Plutella xylostella Caterpillars

Young cabbage plants are sprayed with an aqueous emulsion spray liquorwhich comprises 12.5 ppm of the active compound. After the spray coatinghas dried on, the cabbage plants are populated with 10 caterpillars ofthe first stage of Plutella xylostella and introduced into a plasticcontainer. Evaluation is carried out after 3 days. The reduction in thepopulation in percent and the reduction in the feeding damage in percent(% activity) are determined by comparing the number of dead caterpillarsand the feeding damage on the treated and the untreated plants.

In this test, the compounds of the Tables A1 to A4 and Tables 1 to 48show good activity. Thus, in particular the compounds A1.1 to A4.2 aremore than 80% effective.

Example B5 Activity Against Frankliniella occidentalis

In Petri dishes, discs of the leaves of beans are placed onto agar andsprayed with test solution which comprises 12.5 ppm of active compoundin a spraying chamber. The leaves are then populated with a mixedpopulation of Frankliniella occidentalis. Evaluation is carried outafter 10 days. The reduction in percent (% activity) is determined bycomparing the population on the treated leaves with that of theuntreated leaves.

In this test, the compounds of the Tables A1 to A4 and Tables 1 to 48show good activity. Thus, in particular the compounds A1.1 to A4.2 aremore than 80% effective.

Example B6 Activity Against Diabrotica balteata

Maize seedlings are sprayed with an aqueous emulsion spray liquor whichcomprises 12.5 ppm of active compound and, after the spray coating hasdried on, populated with 10 larvae of the second stage of Diabroticabalteata and then introduced into a plastic container. After 6 days, thereduction in the population in percent (% activity) is determined bycomparing the dead larvae between the treated and the untreated plants.

In this test, the compounds of the Tables A1 to A4 and Tables 1 to 48show good activity. Thus, in particular the compounds A1.1 to A4.2 aremore than 80% effective.

Example B7 Activity Against Tetranychus urticae

Young bean plants are populated with a mixed population of Tetranychusurticae and, after 1 day, sprayed with an aqueous emulsion spray liquorwhich comprises 12.5 ppm of active compound, incubated at 25° C. for 6days and then evaluated. The reduction in the population in percent (%activity) is determined by comparing the number of dead eggs, larvae andadults on the treated and on the untreated plants.

In this test, the compounds of the Tables A1 to A4 and Tables 1 to 48show good activity. Thus, in particular the compounds A1.1 to A4.2 aremore than 80% effective.

1. A compound of the formula (I)

wherein A-B is —CH═CH— or —CH₂—CH₂—; n is 0 or 1; R₁ is C₁-C₁₂alkyl, C₃-C₈cycloalkyl or C₂-C₁₂alkenyl; R₂ and R₃ are either, (i) independently from each other, -Q, —C(═Y)-Q, —C(═Y)—O-Q, —C(═Y)—N(R₆)-Q, —SO₂Q, —SO₂N(R₆)Q or CN; or (ii) together with the nitrogen atom to which they are bound form a three- to ten-membered ring, which may be monocyclic or bicyclic, which may be saturated or unsaturated, and that may contain, in addition to the aforesaid nitrogen atom, one to two hetero atoms selected from the group consisting of N, O and S, and which is either unsubstituted or independently of one another mono- to pentasubstituted with substituents selected from OH, ═O, SH, ═S, halogen, CN, SCN, N₃, NO₂, aryl, C₁-C₁₂alkyl, C₃-C₈cycloalkyl, C₁-C₁₂alkoxy, C₃-C₈cycloalkoxy, C₁-C₁₂haloalkoxy, C₁-C₁₂alkylthio, C₁-C₁₂cycloalkylthio, C₁-C₁₂haloalkylthio, C₁-C₆alkoxy-C₁-C₆alkyl, C₂-C₈alkenyl, C₂-C₆alkenyloxy, C₂-C₆haloalkenyloxy, C₂-C₈alkynyl, C₃-C₆haloalkynyloxy, C₂-C₆alkenylthio, C₂-C₆haloalkenylthio, C₁-C₆alkylsulfinyl, C₃-C₈cycloalkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₃-C₈halocycloalkylsulfinyl, C₂-C₆alkenylsulfinyl, C₂-C₆haloalkenylsulfinyl, C₁-C₆alkylsulfonyl, C₃-C₈cycloalkylsulfonyl, C₁-C₆haloalkylsulfonyl, C₃-C₈halocycloalkylsulfonyl C₂-C₆alkenylsulfonyl, C₂-C₆haloalkenylsulfonyl, phenoxy, phenyl-C₁-C₆alkyl, trialkylsilyl; —C(═O)R₇, —O—C(═O)—R₈, —NH—C(═O)—R₈ and —N(R₉)₂, wherein the two R₉ are independent of each other; or (iii) together are ═C(R₄)R₅; R₄ and R₅ are, independently from each other, -Q, —C(═Y)-Q, —C(═Y)—O-Q, —C(═Y)—N(R₆)-Q, —SO₂Q, —SO₂N(R₆)Q or CN; or R₄ and R₅ are together with the carbon atom to which they are bound, a three- to ten-membered alkylene or a four- to seven-membered alkenylene bridge, wherein one CH₂ group in the alkylene or alkenylene may have been replaced by O, S or NR₉, and which is unsubstituted or mono to tri-substituted; Y is O or S; R₆ is H, C₁-C₈alkyl, C₃-C₈cycloalkyl, C₂-C₈alkenyl, C₂-C₈alkynyl, phenyl, benzyl or —C(═O)R₇; Q is H, unsubstituted or mono- to pentasubstituted C₁-C₁₂alkyl, unsubstituted or mono- to pentasubstituted C₂-C₁₂alkenyl, unsubstituted or mono- to pentasubstituted C₂-C₁₂alkynyl, unsubstituted or mono- to pentasubstituted C₃-C₁₂-cycloalkyl, unsubstituted or mono- to pentasubstituted C₅-C₁₂-cycloalkenyl, unsubstituted or mono- to pentasubstituted aryl, or unsubstituted or mono- to pentasubstituted heterocyclyl; and wherein the substituents of the alkyl, alkenyl, alkynyl, alkylene, alkenylene, cycloalkyl, cycloalkenyl, aryl and heterocyclyl radicals mentioned under Q, R₂, R₃, R₄, R₅ and R₆ are selected from the group consisting of OH, ═O, SH, ═S, halogen, CN, SCN, SF₅, N₃, NO₂, aryl, C₃-C₈cycloalkyl, C₁-C₁₂haloalkyl, C₃-C₈halocycloalkyl, C₁-C₁₂alkoxy, C₃-C₈cycloalkoxy, C₁-C₁₂haloalkoxy, C₁-C₁₂alkylthio, C₁-C₁₂cycloalkylthio, C₁-C₁₂haloalkylthio, C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₆-alkoxy-C₁-C₆-alkoxy, C₂-C₈alkenyl, C₂-C₆alkenyloxy, C₂-C₆haloalkenyl, C₂-C₆haloalkenyloxy, C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₃-C₆alkynyloxy, C₃-C₆haloalkynyloxy, C₂-C₆alkenylthio, C₂-C₆haloalkenylthio, C₁-C₆alkylsulfinyl, C₃-C₈cycloalkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₃-C₈halocycloalkylsulfinyl, C₂-C₆alkenylsulfinyl, C₂-C₆haloalkenylsulfinyl, C₁-C₆alkylsulfonyl, C₃-C₈cycloalkylsulfonyl, C₁-C₆haloalkylsulfonyl, C₃-C₈halocycloalkylsulfonyl C₂-C₆alkenylsulfonyl, C₂-C₆haloalkenylsulfonyl, phenoxy, phenyl-C₁-C₆alkyl, trialkylsilyl; —C(═O)R₇, —O—C(═O)—R₈, —NH—C(═O)—R₈, —N(R₉)₂, wherein the two R₉ are independent of each other, aryl, benzyl, heterocyclyl, aryloxy, benzyloxy, heterocyclyloxy, arylthio, benzylthio and heterocyclylthio; wherein the aryl, heterocyclyl, aryloxy, benzyloxy, heterocyclyloxy, arylthio, benzylthio and heterocyclylthio radicals are unsubstituted or, depending on the possibilities of substitution on the ring, are mono- to pentasubstituted by substituents selected from the group consisting of OH, ═O, SH, ═S, halogen, CN, NO₂, C₁-C₁₂alkyl, C₁-C₁₂hydroxyalkyl, C₃-C₈cycloalkyl, C₁-C₁₂haloalkyl, C₁-C₁₂alkoxy, C₁-C₁₂haloalkoxy, C₁-C₁₂alkylthio, C₁-C₁₂haloalkylthio, C₁-C₆alkoxy-C₁-C₆alkyl, dimethylamino-C₁-C₆alkoxy, C₂-C₈alkenyl, C₂-C₈alkynyl, phenoxy, phenyl-C₁-C₆alkyl; methylenedioxy, —C(═O)R₇, —O—C(═O)—R₈, —NH—C(═O)R₇, —N(R₉)₂, wherein the two R₉ are independent of each other; C₁-C₆alkylsulfinyl, C₃-C₈cycloalkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₃-C₈halocycloalkylsulfinyl, C₁-C₆alkylsulfonyl, C₃-C₈cycloalkylsulfonyl, C₁-C₆haloalkylsulfonyl and C₃-C₈halocycloalkylsulfonyl; R₇ is H, OH, SH, —N(R₉)₂, wherein the two R₉ are independent of each other, C₁-C₂₄alkyl, C₂-C₁₂alkenyl, C₁-C₈hydroxyalkyl, C₁-C₁₂haloalkyl, C₁-C₁₂alkoxy, C₁-C₁₂haloalkoxy, C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkoxy, C₁-C₆alkoxy-C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₁₂alkylthio, C₂-C₈alkenyloxy, C₃-C₈alkynyloxy; aryl, benzyl, heterocyclyl, aryloxy, benzyloxy, heterocyclyloxy; or aryl, benzyl, heterocyclyl, aryloxy, benzyloxy or heterocyclyloxy, which are mono- to tri-substituted in the ring independently of one another by halogen, nitro, C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆haloalkyl or C₁-C₆haloalkoxy; R₈ is H; C₁-C₆alkyl, which is optionally substituted with one to five substituents selected from the group consisting of halogen, C₁-C₆alkoxy, hydroxy and cyano; C₁-C₈-cycloalkyl, aryl, benzyl, heteroaryl; or aryl, benzyl or heteroaryl, which, depending on the possibilities of substitution on the ring, are mono- to trisubstituted by substituents selected from the group consisting of OH, halogen, CN, NO₂, C₁-C₁₂alkyl, C₁-C₁₂haloalkyl, C₁-C₁₂alkoxy, C₁-C₁₂haloalkoxy, C₁-C₁₂alkylthio and C₁-C₁₂haloalkylthio; and R₉ is H; C₁-C₆alkyl, which is optionally substituted with one to five substituents selected from the group consisting of halogen, C₁-C₆alkoxy, hydroxy and cyano; C₁-C₈-cycloalkyl, aryl, benzyl, heteroaryl; or aryl, benzyl or heteroaryl, which, depending on the possibilities of substitution on the ring, are mono- to trisubstituted by substituents selected from the group consisting of OH, halogen, CN, NO₂, C₁-C₁₂alkyl, C₁-C₁₂haloalkyl, C₁-C₁₂alkoxy, C₁-C₁₂haloalkoxy, C₁-C₁₂alkylthio and C₁-C₁₂haloalkylthio; or, if appropriate, an E/Z isomer, E/Z isomer mixture and/or tautomer thereof, in each case in free form or in salt form.
 2. A pesticide composition which contains at least one compound of the formula (I) as described in claim 1 as active compound and at least one auxiliary.
 3. A method for controlling pests comprising applying a composition as described in claim 2 to the pests or their habitat.
 4. A process for preparing a composition as described in claim 2 comprising intimately mixing and/or grinding the active compound with at least one auxiliary.
 5. A method for protecting plant propagation material, wherein the propagation material or the location where the propagation material is planted is treated, comprising applying a composition as described in claim
 2. 6. A plant propagation material treated in accordance with the method described in claim
 5. 